On the polymerization of vinyl‐ and ethynylferrocene

The present paper deals with the polymerization of vinylferrocene and ethynylferrocene in the presence of some initiators or catalysts used for the polymerization of classical vinyl and ethynyl monomers. Ethynylferrocene was polymerized with lauroyl peroxide and B(iso‐C3H7)3 as radical initiators and with substituted phosphine‐transition metal complexes as catalysts, a reaction mechanism being proposed for the last case. Vinylferrocene was polymerized with soluble ZIEGLER systems, e.g., AlEt2Cl/Cu(C5H7O2)2. Attempts to polymerize vinylferrocene with phosphine complexes and ethynylferrocene with soluble ZIEGLER catalyst, Al(iso‐C4H9)3/VO(C5H7O2)2, were unsuccesfully. However, vinylferrocene unlike ethynylferrocene was polymerized with good yields in the presence of the system [–P(C6H5)2]2·Ni(C5H7O2)2. The polymers obtained were investigated with respect to their thermal and electrical properties.