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Electroactive Linear–Hyperbranched Block Copolymers Based on Linear Poly(ferrocenylsilane)s and Hyperbranched Poly(carbosilane)s
Author(s) -
Wurm Frederik,
Hilf Stefan,
Frey Holger
Publication year - 2009
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200900666
Subject(s) - hydrosilylation , copolymer , monomer , polymer chemistry , moiety , dispersity , materials science , polymerization , ferrocene , dendrimer , reactivity (psychology) , comonomer , polymer , chemistry , organic chemistry , electrode , composite material , medicine , electrochemistry , pathology , catalysis , alternative medicine
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]silaferrocenophane 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 ferrocenyldiallylsilane 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.