Abstract
AbstractHexafluoro‐1,3‐butadiene (HFBD), which can be hardly polymerized under radical polymerization conditions, was polymerized with caesium and rubidium compounds as initiators. Among the initiators examined, caesium fluoride, tert‐C4H9OCs, Cs+ (α‐methylstyrene)n2− Cs +, caesium naphthalene (C10H8°Cs+), tert‐C4H9ORb, Rb+ (α‐methylstyrene)n2−Rb+ and rubidium naphthalene (C10H8°Rb+) show surprisingly high activity. Polymerization of HFBD with typical anionic polymerization initiators possessing lithium and sodium as counter cations failed. The ionic radius of the counter cations may thus be important in the anionic polymerization of HFBD. The investigation of the initiation reaction supported the anionic polymerization mechanism. Poly(HFBD) obtained is a white powdery substance which is insoluble in any solvent. Poly(HFBD) possesses a 1,4 microstructure in the main chain as derived from solid‐state 13C NMR and infrared spectra. High thermostability of poly(HFBD) was confirmed by differential scanning calorimetric analysis.
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