Patent GB-1049291-A (GB)
Title: Hydroformylation catalysts and processes relating thereto
IPC: C07C45/50
Filed: 1964-01-27
Abstract: The invention comprises a hydrocarbon soluble complex containing (1) a Co carbonyl and at least one biphyllic ligand including a phosphorus or arsenic atom having three valencies satisfied by alkyl or alkoxy groups; (2) Co in complex bond with CO, a biphyllic ligand including a phosphorus or arsenic atom having three valencies satisfied by alkyl or alkoxy groups, and a ligand derived from a conjugated diolefine and at least partially pibonded to Co.  Catalyst complexes of type (1) may be prepared by treating dicobalt octacarbonyl solution with an appropriate alkyl or alkoxy derivative of phosphorus and then subjecting the product to elevated temperature. The derivative resulting from the first step of the reaction may be isolated as a yellow hydrocarbon-insoluble complex having the formula [Co(CO)3PR3] + [Co(CO)4]-which is unsuitable for use as a catalyst in the oxo process.  Suitable solvents for the first step of the reaction include paraffinic, naphthenic and aromatic hydrocarbons.  Catalyst complexes of type (2) may be prepared by reacting dicobalt octacarbonyl with an excess of conjugated diolefine in the presence of synthesis gas to give a diolefine adduct of cobalt hydrocarbonyl and then reacting this adduct with at least a stoichiometric quantity of an appropriate ligand e.g. trialkyl phosphine to replace one carbon monoxide group. The first stage of the reaction may be conducted at pressures in the range from about 500 to 3000 p.s.i.g. and temperatures in the range from about 200 DEG  to 350 DEG  F.  At least a fivefold excess of synthesis gas to diolefine should be present. In the second stage a stoichiometric excess of the P or As compound, based on the cobalt, is employed and the temperature of the reaction may be in the range from 100 DEG  to 350 DEG  F.  The solvent is removed from the resulting complex by vacuum distillation. Suitable biphyllic ligands are phosphines, phosphites, phosphonites, phosphinites, arsines, arsites and arsenites. Suitable conjugated diolefines are butadiene, isoprene, piperylene and hexadienes.  The catalyst of types (1) and (2) are used in the preparation of hydroxylated and/or carbonyl compounds by reacting an olefine with hydrogen and carbon monoxide in the presence of either of these catalysts.  The reaction is carried out at pressures between 50 and 3000 p.s.i.g. and temperatures between 200 DEG  and 500 DEG  F.  Improved yields are obtained when the molar ratio of hydrogen to carbon monoxide is greater than 1:1 and up to 10:1, alcohols being obtained when the ratio is about 2:1 and aldehydes being obtained when it is about 1:1. Suitable olefines for this reaction are straight and branch chain olefines including mono-olefines, diolefines, aryl substituted olefines and cyclo-olefines. Examples are given for the preparation of catalyst complexes of types (1) and (2), and in which the catalyst complexes of type (1) are used in the " oxo " reaction of 2-methylpentene-1, octene-1 and a C7 olefine mixture, and in which catalyst complexes of type (2) are used in the " oxo " reaction of a C7 olefine mixture, hexene-1 and octene-1. Examples are also given which illustrate the effect in an oxo process of the R radicals being phenyl in the case of catalyst complexes of type (1).  Comparative examples are also given to show that the catalyst precursor is ineffective as a catalyst in the " oxo " -reaction.  A comparative example is also given in which the catalyst complex [Co(HCONH2)x]+ + [Co(CO)4]2- is prepared from formamide and Co2(CO)8 in situ in an " oxo " synthesis.ALSO:Hydroformylation products of unsaturated hydrocarbon polymers having M.W.s from 300 to 1,000,000 and wherein from about 5 to 100% of said unsaturation has been replaced with -CH2OH and/or -CHO groups are obtained by reacting the olefin with H2 and CO in the presence of a hydrocarbon soluble complex containing (1) a CO carbonyl and at least one biphyllic ligand including a P or As atom having three valencies satisfied by alkyl or alkoxy groups; or (2) CO in complex bond with CO, a biphyllic ligand including a P or As atom having three valencies satisfied by alkyl or alkoxy groups and a ligand derived from a conjugated diolefin and at least partially pi-bonded to Co (see Division C2 for preparation).  The reaction may be carried out at pressures of 50 to 3000 p.s.i.g. and temperatures between 200 DEG  and 500 DEG  F. Suitable hydrocarbon polymers include elastomeric polybutadienes, styrene-butadiene rubber, natural rubber and ethylene-propylenediolefin tripolymers.