GB890082A - Compounds containing nickel in internal complex combination and their production - Google Patents

Abstract

Nickel chelate compounds for use as catalysts in the polymerization of acetylene to cyclooctatetraene and the reaction of carbon monoxide with acetylene are prepared by reacting nickel hydroxide and/or nickel carbonate in the absence of a solvent with at least one organic chelate-forming compound, the reaction being carried on with intense mixing until the product is in the form of a paste, the product then being mixed with an inert binding agent such as glue or water-glass and pressed into tablet or string form. In a modification, part of the chelateforming compound is replaced by a substantially stoichiometric amount of a non-chelating alcohol or phenol. Specified chelate-forming compounds include b -diketones, b -acyl acetates, aminophenols and aromatic hydroxyaldehydes. The compounds replacing part of the chelating agents include aliphatic, cycloaliphatic and araliphatic alcohols, phenol and cresols. The complexes are normally obtained in the form of dihydrates which can be dehydrated in vacuo. In Example 4, nickel hydroxide is reacted with ethyl acetoacetate and the plastic product is mixed with a little water-glass, extruded into strings and dried.ALSO:Organic nickel chelate compounds are prepared by reacting nickel hydroxide and/or nickel carbonate in the absence of a solvent with at least one organic chelate-forming compound, the reaction being carried on with intense mixing until the product is in the form of a paste or is in finely-grained form. Complexes obtainable as above described and containing one gram atom of nickel combined with one mole each of two different organic chelate-forming compounds, and dihydrates of these complexes, are claimed per se. In a modification of the above process, part of the chelate-forming organic compound is replaced by a substantially stoichiometric amount of a non-chelating alcohol and/or phenol. The chelate-forming compounds contain two different or identical functional groups such as OH, CO, CHO, NH2 or COOR where R represents a C1-6 alkyl radical or a cycloalkyl or aryl radical, as in b -dicarbonyl compounds, aminophenols and aromatic hydroxy-aldehydes. The nickel reagent and the chelating agents are generally used in molar ratios of about 1 : 2 though a larger excess of the chelating agent may be used. When part of the chelating agent is replaced by an alcohol and/or phenol, the latter may be a mono- or di-hydric aliphatic, cycloaliphatic or araliphatic alcohol or phenol or a cresol, many being specified. Generally, the phenol and/or alcohol and the chelating agent are used in equimolar amounts, and the complexes contain one gram atom of nickel and one mole each of the chelating agent and other reactant. The reactions are suitably carried out in a kneading machine or in a bucket type drier, suitable forms of both being described, and at temperatures from about 0 DEG C. to 90 DEG C. The product is generally first formed as a paste which subsequently becomes a pulverulent mass; a small amount of paraffin oil may be present to prevent dust formation. The product is also normally obtained as a hydrate which may be dehydrated in vacuo. Plastic products may be pressed into desired shapes, e.g. tablets suitably after admixture with a binding agent, e.g. glue or water glass and then dried. The complexes may be used as catalysts for the polymerization of acetylene to cyclo-octatetraene and for carbonmonoxide/acetylene reactions. Examples describe the preparation of complexes from nickel carbonate and/or nickel hydroxide and (1) methylethyl or tert.-butyl aceto acetate, (2) ethyl benzoyl acetate, (3) benzoyl acetone, (4) dibenzoyl methane, (5) salicyl aldehyde, (6) o-aminophenol, (7) a mixture of methyl or ethyl aceto acetate and acetyl acetone, (8) a mixture of acetyl acetone and either benzoyl acetone, dibenzoyl methane, salicyl aldehyde or o-aminophenol, (9) acetyl acetone and methanol, ethanol, propanol, butanol, amyl alcohol, benzyl alcohol, phenol or p-cresol, and (10) acetyl acetone, the products generally being dihydrates sometimes rendered anhydrous by drying.