Polyzwitterions with LCST Side Chains: Tunable Self-Assembly

Macromolecules. 2020 Oct 13;53(19):8267-8275. doi: 10.1021/acs.macromol.0c01708. Epub 2020 Sep 17.

Abstract

Manipulation of self-assembly behavior of copolymers via environmental change is attractive in the fabrication of smart polymeric materials. We present tunable self-assembly behavior of graft copolymers, poly(sulfobetaine methacrylate)-graft-poly[oligo(ethylene glycol) methyl ether methacrylate)-co-di(ethylene glycol) methyl ether methacrylate] (PSBM-g-P(OEGMA-co-DEGMA)). Upon heating the aqueous solutions, the graft copolymers undergo a transition from micelles with PSBM cores to unimers (i.e., individual macromolecules) and then to reversed micelles with P(OEGMA-co-DEGMA) cores, thus demonstrating the tunability of the self-assembling through temperature change. In the presence of salt the temperature response of PSBM is eliminated, and the structure of the micelles with the P(OEGMA-co-DEGMA) core changes. Moreover, for the graft copolymer with long side chains, micelles with aggregation number 2 were formed with a PSBM core at low temperature, which is ascribed to the steric effect of the P(OEGMA-co-DEGMA) shell.