Epoxy-Amine Polymerization\nto Access Poly(β-hydroxyl\namine)s with Active Tertiary Amino Pendant Groups

Epoxy-amine polymerization was investigated as a synthetic\nmethod\nfor developing poly(β-hydroxyl amine)s with active tertiary\namino pendant groups. Primary amines bearing pyridinyl, imidazolyl,\ndimethylamino, diethylamino, and dibutylamino groups, along with controls\nbearing mild groups, were used in the polymerization with diglycidyl\nether of bisphenol A. While optimized solution polymerization was\nestablished by using the primary amines substituted with mild groups,\nonly dibutylamino groups were incorporated as active tertiary amino\npendant groups into thermoplastic polymer without gelation. In bulk\npolymerization, the presence of all additional tertiary amino groups\nled to cross-linking. Model reactions showed two pathways where the\ntertiary amino groups involve cross-linking, which varied depending\non the nucleophilicity and steric effects of the tertiary amino groups.\nThe choice of tertiary amino group and stoichiometric imbalance between\nepoxy and amino monomers affected the physical properties of the resulting\nthermosetting polymers, which possess partially quaternized backbones\nwith β-hydroxyl and active tertiary amino pendant groups.