Site-Selective Trimodular Polymerization to Amino Acid-Based Poly(ether amide)s with Divergent Properties

Amido groups are ubiquitous in natural and synthetic polymers and impart critical physiological and physicochemical properties. Conventional access to backbone-amido polymers, polyamides, generally relies on harsh conditions or highly reactive monomers to form amide bonds during polymerization. Here, we report a mild and atom-economic pathway to poly(ether amide)s (PEAs) through the linear step polymerization of diepoxides and amide-bearing primary diols formed in situ by amino alcohols, mostly derived from natural amino acids, and a reactive solvent, γ-butyrolactone. The unique chemoselectivity of the Lewis pair (organo)catalyst enables preferential activation of primary hydroxyl groups toward epoxy ring opening in this multiprotonic system containing secondary/tertiary hydroxyl and amido groups. The trimodular synthesis and abundant starting materials can be well-utilized for structural diversification and property refinement of PEAs, as showcased by their high interfacial performance in two divergent directions: (1) broad-spectrum protein resistance for the more hydrophilic ones, and (2) robust adhesion on various substrates even after 10 reuse cycles or at liquid nitrogen temperature, for the more hydrophobic ones.