Patent ES-264586-A1 (ES)
Title: Catalyst solution and process of polymerizing therewith
IPC: C08F10/00
Filed: 1961-02-02
Abstract: Conjugated diolefins are polymerized in the presence of a catalyst complex characterised in that it comprises the product of combining (a) the metallic or anhydrous compound form of at least one divalent transition metal the divalent ion of which existing in a state of maximum multiplicity in a weak ligand field contains but one electron in any of its two highest energy penultimate d orbitals, i.e. cobalt, nickel, iron, manganese, chromium, palladium and platinum (b) at least one anhydrous aluminium trihalide in which the halogen is chlorine, bromine or iodine and (c) at least 0.5 mole of a protonacceptor material selected from thiophene, substituted thiophenes, alkyl amines and alkylated aromatic hydrocarbons none of components (a), (b) and (c) containing added materials in which a hydrocarbon group is directly bonded to a metal. The conjugated diene may be butadiene isoprene piperylene 2,3-dimethyl butadiene-1,3 2-ethyl butadiene-1,3 2-phenyl butadiene-1,3 2-isopropyl butadiene-1,3 2-neopentyl butadiene-1,3 or pentadiene-1,3. The polymerization is preferably effected in the presence of inert hydrocarbon solvents and diluents, e.g. benzene, toluene, xylene, butane, butene-1, butene-2, pentane, hexane, heptane, cyclohexane and vinyl cyclohexene-1. Many suitable materials for the preparation of the catalysts are listed and examples describe the polymerization of butadiene in the presence of catalysts formed from (1 and 3) cobaltous chloride, aluminium trichloride, xylene and aluminium powder (2) cobaltous chloride, aluminium trichloride, toluene and aluminium powder (4) cobalt metal, aluminium trichloride and xylene (5) cobalt stearate, aluminium trichloride, toluene and aluminium powder (6) cobaltous chloride, aluminium tribromide and thiophene (7) cobaltous bromide, aluminium trichloride, xylene and aluminium powder (8) cobaltous chloride, aluminium trichloride, tri-n-hexylamine and aluminium powder (9) cobalt perfluoro butyrate aluminium trichloride and xylene (11) cobaltous chloride, aluminium trichloride, thiophene and aluminium powder (12) cobalt sulphonate of a polypropylene-benzene condensate, aluminium trichloride, xylene thiophene and aluminium powder (14) nickelous chloride, aluminium trichloride, thiophene and aluminium powder (15) chromous chloride, aluminium trichloride and thiophene (16) manganous chloride, aluminium trichloride and thiophene (17) ferrous chloride, aluminium trichloride and thiophene (18) platinum dichloride, aluminium trichloride and thiophene (19) cobaltous chloride, aluminium triiodide and thiophene and (20) cobaltous fluoride, aluminium trichloride and thiophene the polymerisation of isoprene in the presence of a catalyst formed from (10) cobaltous chloride, aluminium trichloride, xylene and aluminium powder and the polymerisation of 2,3-dimethyl-butadiene-1,3 in the presence of a catalyst formed from (13) cobaltous chloride, aluminium trichloride, xylene, thiophene and aluminium powder. Catalyst residues may be destroyed by adding water, alcohol, acetone, acetic acid, ethers or other active hydrogen containing compounds, and the products washed with water containing surface active agents, and stabilised, e.g. by the addition of heptylated diphenylamine. The products have a predominantly cis-1,4 structure.ALSO:Catalysts for the polymerization of conjugated dienes comprise the product of combining (a) the metallic or anhydrous compound form of at least one divalent transition metal the divalent ion of which existing in a state of maximum multiplicity in a weak ligand field contains but one electron in any of its two highest energy penultimate d orbitals, i.e. cobalt, nickel, iron, manganese, chromium, palladium and platinum (b) at least one anhydrous aluminium trihalide in which the halogen is chlorine, bromine or iodine and (c) at 0,5 mole of a proton-acceptor material selected from thiophene, substituted thiopenes, alkyl amines and alkylated aromatic hydrocarbons none of components (a), (b) and (c) containing added material in which a hydrocarbon group is directly bonded to a metal. The catalysts may be prepared by fusing the metal components or absorbing one in the other from the vapour phase and thereafter adding the proton-acceptor, or by combining all three components, preferably in the presence of a small amount of powdered aluminium or magnesium. Many components suitable for the preparation of the catalysts are listed and examples describe the preparation of catalysts from (1 and 3) cobaltous chloride, aluminium trichloride, xylene and aluminium powder (2) cobaltous chloride, aluminium trichloride, toluene and aluminium powder (4) cobalt metal, aluminium trichloride and xylene (5) cobalt stearate, aluminium trichloride, toluene and aluminium powder (6) cobaltous chloride, aluminium tribromide and thiophene (7) cobaltous bromide, aluminium trichloride, xylene and aluminium powder (8) cobaltous chloride, aluminium trichloride, tri-n-hexylamine and aluminium powder (9) cobalt perfluorobutyrate, aluminium trichloride and xylene (10) cobaltous chloride, aluminium trichloride, xylene and aluminium powder (11) cobaltous chloride, aluminium trichloride, thiophene and aluminium powder (12) cobalt sulphonate of a polypropylene-benzene condensate, aluminium trichloride, xylene, thiophene and aluminium powder (13) cobaltous chloride, aluminium trichloride, xylene, thiophene and aluminium powder (14) nickelous chloride, aluminium trichloride, thiophene and aluminium powder (15) chromous chloride, aluminium trichloride and thiophene (16) manganous chloride, aluminium trichloride and thiophene (17) ferrous chloride, aluminium trichloride and thiophene (18) platinum dichloride, aluminium trichloride and thiophene (19) cobaltous chloride, aluminium triiodide and thiophene and (20) cobaltous fluoride, aluminium trichloride and thiophene.