Tunable ion-containing polymers from the facile copolymerization of functional polyethers

Complex coacervation phenomenon is driven by pairs of oppositely charged macroions and their self-assembly. Different parameters such as charge density, monomer sequence, polymer architecture, and counter-ions affect self-assembly of these polymers. In this work, we demonstrate a tunable polymer platform from the facile copolymer of functional epoxides that allows for control over each of these parameters independently. Statistical copolymers of propargyl glycidyl ether (PGE) and epichlorohydrin (ECH), with functional alkyne and chloromethyl groups respectively, were synthesized. Molecular weights up to 100 kg/mol with narrow distributions were achieved. Copolymer composition was varied by incorporating increasing ratios of PGE (20-80%) in the polymerization feed. Reactivity ratios were calculated as r_PGE= 0.69 and r_ECH= 1.43 using in situ ¹H NMR kinetic study which confirms the statistical nature of the copolymer. Various charge groups such as imidazole and sulfonate were tethered to the polymer chain via orthogonal chemistry through the chloromethyl and alkyne moieties. We controlled charge density by varying copolymer compositions. Therefore, we have demonstrated a facile approach to charged polymers which we will utilize in the future to study charged polymer self-assembly.