Self-oscillating AB diblock copolymer developed by post modification strategy

We prepared AB diblock copolymer composed of hydrophilic poly(ethylene oxide) segment and self-oscillating polymer segment. In the latter segment, ruthenium tris(2,2′-bipyridine) (Ru(bpy)3), a catalyst of the Belousov-Zhabotinsky reaction, is introduced into the polymer architecture based on N-isopropylacrylamide (NIPAAm). The Ru(bpy)3 was introduced into the polymer segment by two methods; (i) direct random copolymerization (DP) of NIPAAm and Ru(bpy)3 vinyl monomer and (ii) post modification (PM) of Ru(bpy)3 with random copolymer of NIPAAm and N-3-aminopropylmethacrylamide. For both the diblock copolymers, a bistable temperature region (the temperature range; ΔTm), where the block copolymer self-assembles into micelle at reduced Ru(bpy)32+ state whereas it breaks-up into individual polymer chain at oxidized Ru(bpy)33+ state, monotonically extends as the composition of the Ru(bpy)3 increases. The ΔTm of the block copolymer prepared by PM is larger than that by DP. The difference in ΔTm is rationalized from the statistical analysis of the arrangement of the Ru(bpy)3 moiety along the self-oscillating segments. By using the PM method, the well-defined AB diblock copolymer having ΔTm (ca. 25 °C) large enough to cause stable self-oscillation can be prepared. The periodic structural transition of the diblock copolymer in a dilute solution ([Polymer] = 0.1 wt. %) is closely investigated in terms of the time-resolved dynamic light scattering technique at constant temperature in the bistable region. A macroscopic viscosity oscillation of a concentrated polymer solution (15 wt. %) coupled with the periodic microphase separation is also demonstrated.