Patent GB-987423-A (GB)
Title: Production of oligomers of 1,3-dienes
Inventor: LAUTENSCHLAGER HANS
IPC: C07C2/52
Filed: 1962-06-29
Abstract: Oligomers of 1,3-dienes, particularly cyclic olefins, are obtained in the presence of a catalyst containing titanium, chromium, iron or nickel which has been activated prior to the reaction with an olefinic, polyolefinic or acetylenic compound. The catalyst may comprise a chromium halide and an organo-aluminium compound (Specification 849,236), chromium oxide, an acid chloride, amide or anhydride and an organo-aluminium compound (Specification 878,650), a titanium compound and an organo-aluminium compound (Specifications 848,951, 867,017, 860,377 and 892,759), a titanium compound or ferric halide, a metal of Group Ia, IIa, IIb, IIIb, IVa, IVb, Vb or VIIb and a halide of an element of Group IIb, IIIa, IVa or Va, the presence of aluminium or an aluminium halide being essential (Specifications 878,120 and 907,698), and a nickel compound, an organo-metallic compound or metallic hydride and a phosphine or phosphite (Belgian Specification 598,363).  The activating compound may be a hydrocarbon or contain inert groups such as ether, carboxylic ester, nitrile, carboxylic amide, amine, imine, epoxy, aldehyde, ketone or sulphide groups, many being specified, but the preferred compound is the diene to be oligomerized.  This is preferably butadiene; also specified are isoprene, 2,3-dimethylbutadiene, 2-ethylbutadiene, pentadiene-1,3 hexadiene - 2,4,3 - methyl - heptatriene-1,4,6 and octatriene-1,3,6. The activating compound is used in an amount to give a molar ratio to the titanium, chromium, iron or nickel of at least 1:1 and preferably in sufficient excess to form a solvent; alternatively an extraneous solvent, particularly a hydrocarbon or ether, is added.  The activator may be added to the formed catalyst or the catalyst may be formed in the presence of the activator. Solid constituents of the formed catalyst may be removed if desired. Oligomerization is effected at - 50 DEG  to 150 DEG  C. and preferably under pressure if the diene is gaseous.  Specification 935,716 also is referred to.ALSO:Oligomers of 1,3-dienes, particularly cyclic olefins, are obtained in the presence of a catalyst containing titanium, chromium, iron or nickel which has been activated prior to the reaction with an olefinic, polyolefinic or acetylenic compound. The catalyst may comprise a chromium halide and an organo-aluminium compound (Specification 849,236), chromium oxide, an acid chloride, amide or anhydride and an organo-aluminium compound (Specification 878,650), a titanium compound and an organo-aluminium compound (Specifications 848,951, 867,017, 860,377 and 892,759), a titanium compound or ferric halide, a metal of Group IA, IIA, IIB, IIIB, IVA, IVB, VB or VIIB and a halide of an element of Group IIB, IIIA, IVA or VA, the presence of aluminium or an aluminium halide being essential (Specifications 878,120 and 907,698), and a nickel compound, an organo-metallic compound or metallic hydride and a phosphine or phosphite (Belgian Specification 598,363).  The activating compound may be a hydrocarbon or contain inert groups such as ether, carboxylic ester, nitrile, carboxylic amide, amine, imine, epoxy, aldehyde, ketone or sulphide groups, many being specified, but the preferred compound is the diene to be oligomerized.  This is preferably butadiene; also specified are isoprene, 2,3-dimethylbutadiene; 2-ethylbutadiene, pentadiene-1,3, hexadiene-2,4, 3-methyl-heptatriene-1,4,6 and octatriene-1,3,6. The activating compound is used in an amount to give a molar ratio to the titanium, chromium, iron or nickel of at least 1:1 and preferably in sufficient excess to form a solvent; alternatively an extraneous solvent, particularly a hydrocarbon or ether, is added.  The activator may be added to the formed catalyst or the catalyst may be formed in the presence of the activator.  Solid constituents of the formed catalyst may be removed if desired. Oligomerization is effected at -50  DEG C. to 150  DEG C. and preferably under pressure if the diene is gaseous.  Specification 935,716 also is referred to.