Verfahren zur Polymerisation olefinisch ungesaettigter Verbindungen und Verwendung von pi-Olefinkomplexen als Polymerisationsinitiatoren

Ethylenically unsaturated monomeric compounds are polymerized in bulk or in inert organic solvent solution using a catalyst comprising solely at least one p complex of a metal of Group Ib, Vb, VIb or VIIb or of an element having an atomic number from 27 to 78 of Group VIII of the Periodic system, with or without an organic halogen compound or an organic amine. The metal p complexes have the following general formulae:-(Olefine)mMe; (Olefine)mMeXn; (Olefine)mMeXnL0 and (Olefine)mMe(aromatic), where Me is the metal atom; m, n, o are integers; L are neutral ligands, e.g. amines or phosphines and X is a monovalent negatively charged radical, e.g. Cl-, NO3-, CH3COO-, ClO4-, Br- or I-. The term "olefine" includes radicals derived from olefines and the "aromatic" may be benzene and its derivatives. The catalytic activity may sometimes be increased by adding smalll amounts of organic, preferably aliphatic, halogen compounds or organic amines. In the examples:-(1) butadiene is polymerized in bulk using nickel (o)-bis-cyclooctadiene-1,3 or monomethylcyclopentadienyl manganese benzene; (2) isoprene is polymerized in benzene using allyl nickel bromide or diallyl nickel; (3) methyl methacrylate is polymerized using dicyclopentadienyl molybdenum dibromide or [nickel(P(C6H5)3)2]C2H4; (4) styrene is polymerized using silver (cyclo-octadiene-1,5) nitrate and pyridine; (5) styrene and vinyl acetate are copolymerized using copper (cyclo-octadiene-1,3) chloride; (6) acrylic acid and propylene (or isobutylene) are copolymerized in cyclohexane using platinum (hexadiene-1,5) chloride; and (7) butadiene and dibutyl fumarate are copolymerized in benzene using ruthenium (cyclohexadiene-1,3) benzene, or dicyclopentadienyl vanadium iodide, or cyclo-octatetraene chromium di-iodide.