Patent GB-1058680-A (GB)
Title: Process for the oligomerisation and polymerisation of olefins
IPC: C08F4/619
Filed: 1964-08-10
Abstract: Olefines such as mono-olefines and diolefines or mixtures thereof may be oligomerized using p -allyl metal compounds or p -allyl metal halides wherein the metal is a transition metal of Groups IV-VIII. Lewis acids such as organoaluminium compounds and aluminium halides, and Lewis bases such as (a) the alkyl, cycloalkyl, aralkyl or aryl compounds of elements of Group V other than nitrogen, (b) the tri-alkyl, -cycloalkyl, -aralkyl or -aryl esters of elements of Group V other than nitrogen, as well as their triamides and (e) dialkyl sulphoxides may be added.  In the examples, butadiene, ethylene, propylene and butene-2 are separately oligomerized, mostly to dimers; also butene-2 and ethylene; ethylene and propylene; and ethylene and cyclohexene are codimerized.ALSO:Olefines such as mono-olefines and diolefines may be polymerized using p -allyl metal compounds or p -allyl metal halides wherein the metal is from Group IVa to VIIa or VIII of the specified Periodic System.  Lewis acids such as organo aluminium compounds or aluminium halides and Lewis bases such as (a) the alkyl, cycloalkyl, aralkyl or aryl compounds of elements of Group V other than nitrogen, (b) the tri-alkyl, -cycloalkyl, -aralkyl or -aryl esters of elements of Group V other than nitrogen, as well as their triamides and (c) dialkyl sulphoxides, may also be present. In the examples:-(1) ethylene is polymerized using tris-p -allyl chromium, bis-p -allyl chromium iodide or bisp -allyl chromium chloride; (2) butadiene is polymerized using tetra-p -allyl chromium, tris-p -allyl-vanadium, p -allyl-nickel chloride and ethyl aluminium dichloride, tris-p -allyl chromium, tris-p -allyl cobalt, bis-p -allyl cobalt iodide and ethyl aluminium dichloride, bis-p -allyl cobalt iodide and aluminium bromide, bis-p -allyl cobalt chloride and diethyl aluminium chloride or ethyl aluminium dichloride, p -allyl cobalt diiodide, triphenyl phosphine and aluminium bromide; (3) propylene is polymerized using vanadium tetrachloride and p -allyl-magnesium chloride and (4) isoprene is polymerized using p -allyl nickel chloride and ethyl aluminium dichloride.ALSO:Catalysts for the oligomerization and polymerization of olefines comprise p -allyl compounds of metals or p -allyl metal halides wherein the metal is from Group IVA to VIIA or VIII of the specified Periodic System together with a Lewis acid and/or a Lewis base.  The Lewis acids may be organoaluminium compounds or aluminium halides and the Lewis bases may be (a) the alkyl, cycloalkyl, aralkyl or aryl compounds of Group V elements other than nitrogen, (b) the tri-alkyl, -cycloalkyl, -aralkyl or-aryl esters of Group V elements other than nitrogen, as well as their triamides and (c) dialkyl sulphoxides. Many examples are given, the p -allyl compounds or halides used being tris-p -allyl chromium, bis-p -allyl chromium iodide, bis-p -allyl-chromium chloride, tris-p -allyl cobalt, bis-p -allyl cobalt iodide, bis-p -allyl cobalt chloride, p -allyl cobalt di-iodide, p -cyclooctatrienyl-nickel chloride, p -cyclo-octenyl nickel chloride, p -allyl-nickel iodide, p -allyl magnesium chloride, p -pineneyl-nickel bromide, p -allyl nickel bromide, p -crotyl nickel iodide, p -cinanmyl nickel chloride; 1, 2, 3-triphenyl-p -cyclopropenyl nickel bromide; p -allyl palladium chloride, p -allyl nickel chloride, tetra-p -allyl zirconium, tris-p -allyl vanadium and C12 H19 NiCl.