Patent GB-971755-A (GB)
Title: Methods of preparing and using new organo-nickel catalyst complexes
IPC: B01J31/18
Filed: 1961-05-30
Abstract: The invention comprises organo-nickel complexes of general formula <FORM:0971755/C1/1> in which Z1, Z2, Z3 and Z4 are the same or different and are of formula M(OaR1) (OaR2) (OaR3) in which M is phosphorus, arsenic or antimony; a is zero or 1; and R1, R2 and R3 are the same or different hydrocarbon radicals or substituted hydrocarbon radicals in which the substituents comprise oxygen or halogen, and specific compounds claimed are tetrakis (triphenyl phosphite) nickel, tetrakis [tri-(p-methoxy-phenyl) phosphite] nickel, tetrakis [tri-(p-tolyl) phosphite] nickel, tetrakis [tri-(2-ethylhexyl) phosphite] nickel, bis (triphenyl phosphite)-bis-(triethyl phosphite) nickel, and tris (triphenyl-phosphite)-triphenyl phosphine nickel.  The compounds are prepared by reacting a nickel complex of formula (Z1)b(Z2)c(Z3)dNi(CO)4-(b+c+d) with a compound of Z4, wherein Z1, Z2, Z3, and Z4 are as above, and b, c, and d are each zero or one. Substituted or unsubstituted hydrocarbon radicals which may be R1, R2 and R3, are listed, and the carbonyl replacement may be a stepwise process, with or without a solvent, and under an inert gas.  The products may be purified by washing with ketones. and may be used as catalysts in the polymerization of ethylenically unsaturated substituted and unsubstituted hydrocarbons e.g. 1, 3-butadiene, isoprene, chloroprene, piperylene, phenyldiolefines, 2, 3-dichloro-1, 3-butadiene, and 2, 3-dimethyl-1, 3-butadiene.  Specifications 701,106 and 716,133 are referred to.ALSO:Ethylenically unsaturated hydrocarbons and halogenated hydrocarbons are polymerized in the presence of a catalyst comprising an organonickel complex of general formula <FORM:0971755/C3/1> in which Z1, Z2, Z3 and Z4 are the same or different and are of the formula M(OaR1) (OaR2) (OaR3) in which M is phosphorus, arsenic or antimony; a is zero or 1; and R1, R2 and R3 are the same or different hydrocarbon radicals or substituted hydrocarbon radicals in which the substituents comprise oxygen or halogen, and specific examples are tetrakis (triphenyl phosphite) nickel, tetrakis [tri-p-methoxyphenyl) phosphite] nickel, tetrakis [tri-(p-tolyl) phosphite] nickel, tetrakis [tri-(2-ethylhexyl) phosphite] nickel, bis (triphenylphosphite)-bis (triethyl phosphite) nickel, and tris (triphenyl phosphite)-triphenylphosphine nickel (see Division C2). 1, 3-butadiene, isoprene, chloroprene, 1, 3-pentadiene, phenyldiolefines; 2, 3-dichloro-1, 3-butadiene and 2, 3-dimethyl-1, 3-butadiene are mentioned as suitable compounds. The catalysts may be in admixture with nickel complexes containing carbonyl groups and the reaction may be continuous or batch type at temperatures between 70 and 200 DEG C., with preferred pressures of 15.75 to 29.75 kilograms per square cm. gauge.  Specifications 701,106 and 716,133 are referred to.ALSO:Conjugated diolefins are polymerized (to dimers and upwards) to form cyclic polyolefins in the presence of a catalyst comprising an organo-nickel complex of general formula <FORM:0971755/C4-C5/1> in which Z1, Z2, Z3 and Z4 are the same or different and are of the formula M(OaR1) (OaR2)(OaR3) in which M is phosphorus, arsenic or antimony; a is zero or 1; and R1, R2 and R3 are the same or different hydrocarbon radicals or substituted hydrocarbon radicals in which the substituents comprise oxygen or halogen. Examples describe the polymerization of 1,3-butadiene with tetrakis (triphenyl phosphite) nickel or bis (triphenyl phosphite) bis (triethyl phosphite) catalysts to a mixture of cyclo - octa - 1,5 - diene, vinylcyclohexene and higher boiling material, and isoprene with a tetra (triphenylphosphite) nickel catalyst to dimethylcyclo-octadiene.  Other specific compounds mentioned are tetrakis (tri p-methoxy-phenyl phosphite) nickel, tetrakis (tri-p-tolyl phosphite nickel), tetrakis [tri (2-ethylhexyl) phosphite] nickel and tris (triphenyl phosphite) triphenyl phosphine nickel.  Other monomers which are mentioned are 1,3-pentadiene, phenyldiolefins, 2,3 - dichloro - 1,3 - butadiene and 2,3-dimethyl-1,3 butadiene and the processes may be batch-wise or continuous with a catalyst concentration of from 0.5 to 1.5% at 70-200 DEG  C. and 15.75-70 kg/cm.2.g. Specifications 701,106 and 716,133 are referred to.