화학공학소재연구정보센터
Macromolecules, Vol.40, No.23, 8195-8204, 2007
Hyperbranched poly(ferrocenylphenylenes): Synthesis, characterization, redox activity, metal complexation, pyrolytic ceramization, and soft ferromagnetism
Hyperbranched poly(ferrocenylphenylenes) (hb-PFPs) with high molecular weights were synthesized by the copolycyclotrimerizations of (E,E)-1,1'-bis[2-(4-ethynylphenyl)vinyl]ferrocene (1) with (E)-1-[2-(4-ethynylphenyl)vinyl]ferrocene (2) catalyzed by TaCl5-Ph4Sn at room temperature in high yields (up to 97%). Effects of reaction conditions, such as monomer and catalyst concentrations, reaction time and molar feed ratio (r(1/2)), on the copolycyclotrimerization were investigated. Solubility of the copolymer is decreased with an increase in its content of diyne component (N-1/N-2). The hb-PFPs were characterized by IR, NMR, UV, CV and TGA analyses. The copolymers are redox active, whose oxidation potentials are decreased with an increase in N1/N2. They are thermally stable, losing similar to 5% of weights when heated to 384-400 degrees C and retaining similar to 70% of weights when pyrolyzed at 1200 degrees C. The complexation with cobalt carbonyl further metallizes the hb-PFPs and the pyrolytic ceramization of the cobalt-polymer complexes yields soft ferromagnetic ceramics with high magnetizability (M-s up to similar to 126 emu/g) and low coercivity (H-c down to similar to 0.068 kOe).