Patent GB-1061002-A (GB)
Title: Polymerization catalyst and use thereof
IPC: C08F36/04
Filed: 1964-02-11
Abstract: Metal chelate compounds comprising a trivalent ion of a metal of Group III (B) of the Periodic Table on pp. 56 and 57 in Langs' Handbook of Chemistry, eighth edition, having an atomic number of from 21 to 71, and a bidentate organic ligand containing up to and including 20 carbon atoms wherein the functional groups are tertiary nitrogen, formyl, carbonyl, oxy, alkoxy, alkoxycarbonyl, amino, alkamino, and/or hydroxyl, and are separated by no more than 5 carbon atoms are made by reacting the metal or salt of the metal with organic compounds providing the desired bidentate ligands.  The preferred metals are lanthanium and cerium. Suitable organic chelating compounds are salicylaldehyde, 2-hydroxy-1-and 2 - hydroxy - 3 - naphthaldehyde, 21 - hydroxybutyro - or aceto - or propio - phenone, o - aminophenol, N - methyl or N - ethyl o-aminophenol, ethyl, propyl, or butyl salicylate, 2 - hydroxyquinoline, 8 - hydroxyquinoline, acetylacetone, benzoylacetone, propionyl acetone, isobutyrlacetone, valerylacetone, ethyl-acetylacetone, acetic acid, propionic acid, valeric acid, hexanoic acid, 2-ethylhexanoic acid, lauric acid, stearic acid, pyrocatechol, ethylene or propylene or trimethylene or tetra-methylene glycol, oxalic, malonic, maleic, succinic, or o-phthalic acid, o-hydroxyanisole, o-hydroxyethyl phenyl ether, 5-methylsalicyl-aldehyde, 5 - cyclohexylsalicylaldehyde, 4-methoxy salicylaldehyde, and 4 - methyl - 8 -hydroxyquinoline. Exemplified metal chelate compounds are Ce (t-butylsalicylaldehyde) Cl2, cerous 5 - cyclohexylsalicylaldehyde chloride, cerous 2 - hydroxyquinolinato chloride, cerous 8 - hydroxyquinolinato chloride, cerous 2-acetylphenolato chloride, cerous o-aminophenolato chloride, cerium tris (8-hydroxyquinolinate), lanthanium tris (8-hydroxyquinolinate), cerium tris (2-ethylhexanoate), cerous chloride oxalate, cerous bromide oxalate, and dysprosium tris (2-ethylhexanoate).ALSO:A polymerization catalyst comprises the reaction product of (1) a metal chelate comprising a trivalent ion of a metal of Group III (B) of the Periodic Table having an atomic number of from 21 to 71 and a bidentate organic ligand containing up to and including 20 carbon atoms, wherein the functional groups are tertiary nitrogen, formyl, carbonyl, oxy, alkoxy, alkoxycarbonyl, amino, alkamino, and/or hydroxyl and are separated by no more than 5 carbon atoms, (2) from 0.1 to 10 moles of halide ion per mole of Group III (B) metal ion, and (3) from 1 to 400 moles per mole of Group III (B) metal ion, of an alkyl aluminium compound of the formula  R(3- n)AlHn, where R is an alkyl group containing from 1 to 15 carbon atoms and n is 0, 1 or 2. Component (2) of the catalyst can be introduced as a halide of a component (1) compound or as an alkyl aluminium halide.  The catalyst is used to polymerize, either in bulk or organic solvent, one or more dienes.  Specified dienes are butadiene-1,3, isoprene, 2,3-dimethyl or 2,3-dibutyl, or 2-ethyl, or 2-hexyl, or 2-decyl-1,3-butadiene. The Specification contains an extensive list of suitable catalyst components. A representative list of catalysts exemplified are, triisobutyl aluminium and cerium salicylaldehyde dichloride, triisobutyl Al and Ce (t-butylsalicylaldehyde) Cl2, triisobutyl Al and 5 - cyclohexylsalicylaldehyde chloride, diisobutyl Al hydride and cerous t-butyl-salicylaldehyde chloride, triisobutyl Al and cerous (t-butylsalicyaldehyde) dichloride, tri-isobutyl Al and Ce (cyclohexylsalicylaldehyde)xCl3- x, where x is an integer less than 3, tri-isobutyl Al and cerous 2-hydroxyquinolinato chloride, triisobutyl Al and cerous 8-hydroxyquinolinato chloride, triisobutyl Al and cerous 2-acetylphenolato chloride, triisobutyl Al and cerous o-aminophenolato chloride, diisobutylaluminium chloride and lanthanum tris-(8-hydroxyquinolinate), triisobutyl Al bromide and triisobutylaluminium and cerium tris-(2-ethylhexanoate) and tri-isobutyl Al and cerous chloride oxalate. The polymerizate is recovered by conventional low-pressure techniques.  The polymerized 1,3-dienes have a high cis-1,4-structure.