A route toward multifunctional polyurethanes using triple click reactions

The aliphatic polyurethane with pendant alkyne, perfluorophenyl, and anthracene moieties (PU-anthracene) was prepared from polycondensation of anthracene, alkyne, and perfluorophenyl functional-diols with hexamethylenediisocyanate in the presence of dibutyltindilaurate (DBTL) in CH₂Cl₂ at room temperature for 10 days. Thereafter, the PU-(anthracene-co-alkyne-co-perfluorophenyl) (M_n,GPC = 15,400 g/mol, M_w/M_n= 1.37, relative to PS standards) was sequentially clicked with benzyl azide, octylamine, and 4-(2-hydroxyethyl)-10-oxa-4-azatricyclo[5.2.1.02,6]dec-8-ene-3,5-dione (adduct alcohol) via copper-catalyzed azide-alkyne cycloaddition, active ester substitution and Diels-Alder reactions, respectively, to finally yield PU-(hydroxyl-co-benzyltriazole-co-octylamine). The PUs were characterized using ¹H NMR, GPC, and DSC.