Abstract: The present invention is directed to a process for the production of polyisocyanate mixtures containing isocyanurate groups and uretdione groups in a molar ratio of about 1:9 to 9:1 by oligomerizing a portion of the isocyanate groups of hexamethylene diisocyanate using trialkyl phosphines and/or peralkylated phosphorus acid triamides as the catalysts which accelerate the dimerization and trimerization of isocyanate groups, terminating the reaction at the desired degree of oligomerization by the addition of a catalyst poison and removing unreacted hexamethylene diisocyanate to a residual content of at most 0.5% by weight, characterized in that, before addition of the catalyst, the hexamethylene diisocyanate starting material is freed from carbon dioxide to a residual content of less than 20 ppm (weight).

Abstract: The present invention is directed to a process for the preparation of modified polyisocyanates containing uretdione and isocyanurate groups by the oligomerization of a portion of the isocyanate groups of organic diisocyanates containing (cyclo)aliphatically-bound isocyanate groups in the presence of organic phosphines of catalysts followed by termination of the oligomerization reaction at the desired degree of oligomerization by the addition of a catalyst poison and removal, by distillation, of at least a portion of the excess, unreacted starting diisocyanate, characterized in that(a) about 0.1 to 10% of the isocyanate groups present in the starting diisocyanate are converted into urethane groups by the addition of at least one alcohol before and/or during the oligomerization reaction, and(b) the distillation residue obtained after removal of the excess starting diisocyanate is heated to temperatures of at least 50.degree. C.