Patent GB-892759-A (GB)
Title: Production of liquid oligomers of 1, 3-dienes
Inventor: WITTENBERG DIETMAR
IPC: C07C2/46
Filed: 1960-12-20
Abstract: A catalyst for the polymerization of 1, 3-dienes to oligomers, consists of (1) a titanium compound, (2) an organo-aluminium halide and (3) a metal of Group 1a, 2a, 2b, 3a or 3b, of the periodic system, an alkali or alkaline earth metal salt, an amine, ether, thioether and/or an organic phosphine.  The titanium compound (1) may be a tetra-alkylate or -cycloalkylate, a tri- or tetrahalide and ester halide or organo halide.  The ogano-aluminium halide has the formula A12RnX6-n where R is aliphatic or aromatic, X is halogen and n is 1-5 and may be previously complexed with component (3) where this is a complexing agent.  The salts of alkali or alkaline earth metals are preferably the halides, hydrides and C1-C4 carboxylates. Where an organic compound is used as component (3) this preferably contains aliphatic, cycloaliphatic, araliphatic, or aromatic hydrocarbon radicals or the functional group may be part of a heterocyclic ring; other substituents may be present, e.g. carbonyl, carboxyl, cyano, carboalkoxy and aromatic halogen. Many suitable components (3) are specified.  The mol. ratio of (1): (2): (3) may be 1 :   2 :   1, e.g. 1 : 3-10: 1,5-50. Solvents may be used, e.g. hydrocarbons and halohydrocarbons and the catalyst may be "developed" by mixing all components in a ball mill or vibratory mill in the solvent or by mixing two components in the solvent and then adding the third.  If a suspension is obtained this may be filtered and the solution used as catalyst.  The catalyst may be destroyed at the end of the reaction by adding a small amount of water or an alcohol or a large amount of acetone.ALSO:The polymerization of 1,3-dienes to oligomers, principally cyclic polyolefins, is effected in the presence of (1) a titanium compound, (2) an organo-aluminium halide and (3) a metal of Group 1a, 2a, 2b, 3a or 3b, of the Periodic System, an alkali or alkaline earth metal salt, an amine, ether, thioether and/or an organic phosphine.  Specified dienes are butadiene which yields cyclooctadiene and cyclodecatriene, isoprene, 2,3-dimethylbutadiene and cyclohexadiene and may be used in admixture with inert substances.  The titanium compound (1) may be a tetra-alkylate or -cycloalkylate, a tri- or tetrahalide and ester halide or organic halide.  The organo-aluminium halide has the formula Al2RnX6-n where R is aliphatic or aromatic, X is halogen and n is 1-5 and may be previously complexed with component (3) where this is a complexing agent. The salts of alkali or alkaline earth metals are preferably the halides, hydrides and C1-C4 carboxylates. Where an organic compound is used as component (3) this preferably contains aliphatic, cycloaliphatic, araliphatic, or aromatic hydrocarbon radicals or the functional group may be part of the heterocyclic ring; other substituents may be present, e.g. carbonyl, carboxyl, cyano, carboalkoxy and aromatic halogen.  Many suitable components (3) are specified.  The mol ratio of (1) : (2) : (3) may be 1 : \sF 2 : \sF 1, e.g. 1 : 3-10 : 1.5-50. Solvents may be used, e.g. hydrocarbons and halohydrocarbons and the catalyst may be "developed" by mixing all components in a ball mill or vibratory mill in the solvent or by mixing two components in the solvent and then adding the third.  If a suspension is obtained this may be filtered and the solution used as catalyst.  Suitable conditions are - 10 DEG C. to 150 DEG C. and reduced pressure to 10 atmospheres, normal pressure being preferred.  The catalyst may be destroyed at the end of the reaction by adding a small amount of water or an alcohol or a large amount of acetone.