Patent GB-1061482-A (GB)
Title: Linear octatrienes and process for obtaining thereof
IPC: C07C11/21
Filed: 1963-12-13
Abstract: Linear dimers of open chain diolefinic compounds are prepared by polymerizing the diolefinic compounds at 70 DEG  to 160 DEG  C. in the presence of a zerovalent nickel catalyst and a phenolic or alcoholic compound as cocatalyst, the nickel catalyst being present in an amount of 0.5 to 5.0% by weight of the diolefinic compound and the cocatalyst being present in an amount of 10 to 35% by weight of the diolefinic compound.  The nickel catalysts have the general formulae (I) [(RO)3P]n Ni(CO)4-n (II) (R3P)n Ni(CO)4-n (III) (R3Sb)n Ni(CO)4-n (IV) (R3Ag)n Ni(CO)4-n wherein R is alkyl, aryl or a heterocyclic radical and n is 1 or 2.  Alternative nickel catalysts used have the general formula An-Ni-B2, wherein n is 1 or 2, A is triphenyl phosphine, triphenylphosphite or 1-methyl 4 - phospha 3-5-8 trioxabicyclo (2.2.2) octane and B is cinnamonitrile, acrylonitrile, fumaronitrile or acrolein.  Phenol cocatalysts used include mono and polynuclear mono and polyphenols and examples specified are phenol; o-, m- and p-cresol; 2-xylenol; 3,4-xylenol; 3,5-xylenol and p-methoxyphenol.  Alcohol cocatalysts used have 3 to 18 carbon atoms and may be primary, secondary or tertiary, aliphatic or alicyclic alcohols, e.g. propyl, butyl, hexadecyl alcohols and menthol. Starting materials specified are 1,3-butadiene; 2-methyl 1,3-butadiene; 2,3-dimethyl 1,3-butadiene; 2-chloro-1,3-butadiene; 2,3-dichloro 1,3-butadiene, 1,3-pentadiene, phenyl diolefins; 2,4-hexadiene and chlorofluoro - 1,3 - butadienes.  Polymerization takes place preferably at 100 DEG  to 130 DEG  C., in presence of a solvent and at atmospheric to 1790 p.s.i.g.  Solvents used include dicyclopentadiene alone or mixed with benzene or 1,5-cyclooctadiene; and tetrahydrofuran, toluene, p-cymene, and benzene alone or in admixture with 1 : 5 cyclooctadiene.  A dehydrating agent, e.g. ethylene oxide, calcium carbide and calcium sulphate may be incorporated into the reaction mixture. Oxygen must be excluded from the reaction mixture.  Up to 0.2% of a polymerization inhibitor, e.g. p-tertiarybutyl catechol based upon the weight of the starting material may be added.  The product mixture may be fractionally distilled to obtain 1,3,6-octatriene, 1,5-cycloocatadiene and a binary mixture of 1,3,7-octatriene and 4 vinyl-1-cyclohexene which may be separated by liquid thermal diffusion (see Division B1). Minor amounts of 2,4,6-octatriene and 2,6-octadiene may be present in the product. The Figure (not shown) indicates the method of separating the desired product fractions from the mixture thereof.ALSO:Halogenated octatrienes are prepared by passing halogenated dienes, e.g. 2-chloro-1,3-butadiene or chlorofluoro-1,3-butadienes over a zerovalent nickel catalyst and a phenolic or alcoholic compound as cocatalyst at 70 DEG  to 160 DEG C.  The nickel compounds have the general formulae (I)  [(RO)3P]n Ni(CO)4-n  (II)  (R3P)n Ni(CO)4-n  (III)  (R3Sb)n Ni(CO)4-n  or (IV) (R3As)n Ni(CO)4-n wherein R is alkyl, aryl or a heterocyclic radical and n is 1 or 2. Alternative catalysts have the general formula AnNiB2, wherein n is 1 or 2, A is triphenyl phosphine, triphenyl phosphite or 1-methyl - 4 - phosphor - 3,5,8 - trioxabicyclo - (2,2,2) - octane and B is cinnamonitrile, acrylonitrile, fumaronitrile or acrolein.  The preparation of 1-methyl-4-phosphor-3,5,8 -tri-oxabicyclo-[2,2,2]-octane is described.ALSO:Linear dimers of open chain diolefinic compounds are prepared by polymerisation in presence of a zero-valent nickel catalyst and a phenolic or acoholic compound as cocatalyst, the nickel catalyst being present in an amount of 0.5 to 5.0% by weight of the diolefinic compound and the cocatalyst being present in an amount of 10 to 35% by weight of the diolefinic compound.  The nickel catalysts used have the general formulae  .(I).[(RO)3P]n.Ni(CO)4-n .(II).(R3P)n.Ni(CO)4-n .(III).(R3Sb)n.Ni(CO)4-n .(IV).(R3As)n.Ni(CO)4-n  Wherein R is alkyl, aryl or a heterocyclic radi cal and n is 1 or 2.  Alternative nickel natalysts used have the general formula An-Ni-B2 wherein n is 1 or 2, A is triphenyl phosphine, triphenylphosphite or 1-methyl 4-phospha-3,5,8 trioxabicyclo (2.2.2) octane and B is cinna monitrile, acrylonitrile, fumaronitrile or acro lein.  Phenol cocatalysts used include mono and poly-nuclear mono- or polyphenols and samples specified are phenol; o, m, p cresol; 2 xylenol; 3,4 xylenol; 3,5 xylenol and p-meth onyxylenol.  Alcohol cocatalysts used have 3 to 18 carbon atoms and may be primary, secondary or tertiary aliphatic or alicyclic alcohols, e.g. propyl, butyl, hexadecyl alcohols and methol.  The linear octatriene are separated from liquid mixtures thereof with other hydro carbons, e.g. 4 vinyl-1 cyclohexane; p xylene and 1,5 cyclooctadiene by thermal diffusion.  The liquid mixture is fed through an inlet port into the centre portion of an annular zone defined by two vertical concentric tubes, the outer tube being provided along its length with (a) sampling ports and (b) heating means in the form of electrical resistance winding.  Water is passed upwardly at a constant rate through the inner tube and the linear octatrienes may be taken off through the upper sampling ports and the residual hydrocarbons from the bottom of the column.  The column may be sampled continuously.