Patent GB-840910-A (GB)
Title: Improvements in or relating to the polymerisation of monoethylenically unsaturated monomers
IPC: C08F4/12
Filed: 1958-04-08
Abstract: Addition polymers are made from monoethylenically unsaturated monomers (containing polar radicals which do not have ionizable hydrogen atoms) by polymerization under substantially anhydrous conditions in a liquid aliphatic polar solvent containing no ionizable hydrogen atoms, and in the presence of a catalyst system resulting from the admixture of (1) a compound containing at least one metal of Group IVa, Va and VIa of the Periodic Table, or iron, silver and manganese, said metals being directly attached to one or more of the following: a halogen, oxygen or a radical of formula -OR, where R is a hydrocarbon residue, and (2) a reducing compound containing a metal atom attached directly by a single bond to a trigonal or tetrahedral carbon atom.  The monomer may be vinyl chloride, vinylidene chloride, acrylonitrile, methyl acrylate, vinyl esters such as pivalate, stearate, benzoate, formate and acetate, methyl methacrylate, vinyl ethyl ether, vinyl isobutyl ether, allylidene diacetate or 4-vinyl-pyridine.  The polar solvent may be an ester such as methyl, ethyl or butyl acetate and diethyl carbonate, a nitrile such as acetonitrile or propionitrile, an ether such as 1,4 - dioxane, tetrahydrofuran or diethyl ether or an amide such as dimethylformamide or dimethylacetamide.  Catalyst components specified include titanium and vanadium 4-, 3-, 2-chlorides and oxychloride, ferric bromide, chromium chloride, manganese bromide, molybdenum chloride, silver oxide, 2-ethyl hexyl vanadate, tetraisobutyl and tetraisopropyl titanates and tetraethyl zirconate; aluminium tri - isobutyl, isobutyl dichloride, isobutyl dibutoxide and diisobutyl butoxide, sodium naphthalene, zinc diisobutyl, lithium aluminium tetradecyl, lithium butyl and ethyl magnesium bromide.ALSO:Polymerization (see Group IV (a)) is effected in a liquid aliphatic polar solvent containing no ionizable hydrogen atoms and in the presence of a catalyst system resulting from the admixture of (1) a compound containing at least one metal of Group IVa, Va and VIa of the Periodic Table, or iron, silver and manganese, said metals being directly attached to one or more of the following: a halogen, oxygen or a radical of formula -OR, where R is a hydrocarbon residue; and (2) a reducing compound containing a metal atom attached directly by a single bond to a trigonal or tetrahedral carbon atom.  The polar solvent may be an ester such as methyl, ethyl or butyl acetate and diethyl carbonate, a nitrile such as acetonitrile or propionitrile, an ether such as 1,4-dioxane, tetrahydrofuran or diethyl ether or an amide such as dimethylformamide or dimethylacetamide, Catalyst components specified include titanium and vanadium 4-, 3-, 2-chlorides and oxychlorides, FeBr3, CrCl3, MnBr2, MoCl5, Ag2O, 2-ethylhexyl vanadate, tetraisobutyl and tetraisopropyl titanates and tetraethyl zirconate, aluminium tri-isobutyl, isobutyl dichloride, isobutyl dibutoxide and diisobutyl butoxide, sodium naphthalene, zinc diisobutyl, lithium aluminium tetradecyl, lithium butyl and ethyl magnesium bromide.