Patent GB-907698-A (GB)
Title: Production of oligomers of 1,3-dienes
Inventor: MUELLER HERBERT
IPC: C07C2/46
Filed: 1961-01-10
Abstract: Catalysts for the oligomerization of 1,3-dienes are obtained by mixing (a) an iron (III) halide or a titanium compound, (b) a metal of Group Ia, IIa, IIb, IIIa, IIIb, IVa, IVb, Vb or VIIb of the periodic system and (c) a halide of an element of Group IIb, IIIa, IVa or Va of the periodic system one of components (b) and (c) being aluminium or an aluminium halide.  The titanium compound may be a titanium (IV) acid ester, titanium halide, titanium (IV) ester halide or organotitanium halide.  Specified metals are lithium, sodium, potassium, beryllium, magnesium, calcium, strontium, barium, boron, aluminium, gallium, indium, thallium, lead, titanium, vanadium, manganese and cerium.  Specified halides are boron trichloride, aluminium chloride, aluminium bromide, aluminium iodide, gallium bromide, indium chloride, thallium chloride, carbon tetrachloride, silicon tetrachloride, tin tetrachloride, zinc chloride, zinc iodide, cadmium chloride and antimony trichloride.  The catalysts may also comprise substances which form complexes with the halides, e.g. aluminium chloride, zinc chloride, tin tetrachloride, antimony trichloride, alkali and alkaline earth metal halides, hydrides, cyanides and fatty acid salts, ethers, thioethers, amines and organic phosphines, many suitable compounds being listed.  The catalysts are preferably aged before use, and may subsequently be destroyed by adding water, methanol, ethanol or acetone.  Specification 878,120 is referred to.ALSO:1,3-Dienes are oligomerised by reacting in the presence of a catalyst formed by mixing (a) an iron (III) halide or a titanium compound, (b) a metal of Group Ia, IIa, IIb, IIIa, IIIb, IVa, IVb, Vb or VIIb of the Periodic System and (c) a halide of an element of Group IIb, IIIa, IVa or Va of the Periodic System one of components (b) and (c) being aluminium or an aluminium halide. Specified dienes are butadiene, isoprene, 2,3-dimethyl butadiene and cyclohexadiene-1,3.  The process may be effected batchwise or continuously, in the presence of liquid media, e.g. benzene, toluene, xylene, ethyl benzene, cumene, chlorobenzene, heptane, cyclohexane, isooctane or cyclododecatriene-1,5,9.  The catalysts may also comprise substances which form complexes with halogen compounds, e.g. aluminium chloride, zinc chloride, tin tetrachloride, antimony trichloride, alkali and alkaline earth metal halides, hydrides, cyanides and fatty acid salts, ethers, thioethers, amines and organic phosphines.  Many suitable catalyst forming components are specified and examples describe the oligomerisation of butadiene in the presence of catalysts formed from (1) titanium tetrachloride, zinc and aluminium trichloride, tribromide and triiodide using as complexing agents anisol, lithium chloride, potassium iodide, magnesium iodide, sodium hydride, diphenylene oxide, quinoline, triphenyl phosphine and diethyl ether; (2) titanium tri- or tetrachloride, aluminium, zinc chloride and sodium chloride; titanium tetrachloride and aluminium chloride with (3) sodium and sodium chloride, (4) beryllium, (5) magnesium, (6) calcium, (8) gallium and sodium chloride, (9) lead and sodium chloride, (12) cerium, (16) cadmium, (18) tin and sodium chloride, (19) manganese and diphenylene sulphide, (20) an aluminium/vanadium alloy and sodium chloride, and (25) lithium, magnesium and sodium chloride; titanium tetrachloride and aluminium with (7) carbon tetrachloride and sodium chloride, (10) tin tetrachloride and sodium chloride, (11) antimony trichloride, (14) boron trichloride, (15) bismuth trichloride, and (17) silicon tetrachloride and sodium chloride; (13) titanium tetrachloride, zinc and aluminium tribromide; aluminium chloride and sodium chloride with (21) titanium tetrabromide and titanium, (22) diethoxy dichloro titanium and zinc, (23) titanium tetrafluoride and zinc, (24) ferric chloride and aluminium, and (27) C6H5TiCl2.2AlCl3 and zinc; and the oligomerisation of isoprene in the presence of a catalyst formed from (26) titanium tetrachloride, aluminium and carbon tetrachloride.  The products may be cyclic, polycyclic and open chain compounds and include cyclododecatriene - 1,5,9, cyclooctadiene - 1,5, 1 - vinyl hexene-3 and other oligomers containing 3, 6 and 8 butadiene units. Specification 878,120 is referred to.