Abstract: Essentially linear polyethylenepolyamines are prepared by reacting monoethanolamine with ethylenediamine in the presence of an intercalatively catalytically active tetravalent zirconium polymeric reaction product of an organo phosphonic acid or an ester thereof with a compound of tetravalent zirconium reactive therewith, such as zirconium trimethylene diphosphonate prepared by reacting trimethylenediphosphonic acid wth zirconyl chloride.

Abstract: An aminomethylation reaction is disclosed wherein polymeric polyamines are produced. Polymeric polyolefins such as polybutadiene, ammonia, primary or secondary amines, and synthesis gas are reacted in the presence of a catalyst system comprising a ruthenium-containing catalyst, such as triruthenium dodecacarbonyl, and dimethyl formamide as a solvent.The use of a two-phase solvent mixture consisting of N,N-dimethylformamide plus a hydrocarbon is particularly advantageous in that:(1) The aminomethylation selectivity is improved and few side reactions results;(2) The two-phase liquid product mixture obtained, allows easy separation of product polyamine from ruthenium-containing catalyst.