FIELD: industrial organic synthesis. SUBSTANCE: mixtures of 4,4'- and 2,4'-isomers of aromatic polyamines of general formula: 
, where A and B denote phenylene radicals having 1,4-substituents independent from each other and selected from (C1- C20)-alkyl radicals and halogen atoms, with elevated content of 4,4'-isomers are obtained by reaction of o- toluidine with formaldehyde or its precursor at 130-170 C in presence of heterogeneous interaction catalyst selected from group comprising (i) one or several oxides of group 3-10 elements excepting vanadium oxides, which can be acid activated; (ii) if necessary, acid-activated clay doped by impregnation or ion-exchange with at least one group 2-13 elements; and (iii) one or several optionally acid activated stratified silicates with acidity below pKa = 1.5. EFFECT: increased selectivity of reaction. 6 cl, 6 tbl, 14 ex
