Overcoming Surfactant-Induced Morphology Instability of Noncrosslinked Diblock Copolymer Nano-Objects Obtained by RAFT Emulsion Polymerization.

RAFT emulsion polymerization techniques including polymerization-induced self-assembly (PISA) and temperature-induced morphological transformation (TIMT) are widely used to produce noncrosslinked nano-objects with various morphologies. However, the worm, vesicle and lamellar morphologies produced by these techniques typically cannot tolerate the presence of added surfactants, thus limiting their potential applications. Herein we report the surfactant tolerance of noncrosslinked worms, vesicles, and lamellae prepared by RAFT emulsion polymerizations using poly(di(ethylene glycol) ethyl ether methacrylate- co - N -(2-hydroxypropyl) methacrylamide) (P(DEGMA- co -HPMA)) as a macromolecular chain transfer agent (macro-CTA). Significantly, these P(DEGMA- co -HPMA) nanoparticles are highly stable in concentrated solutions of surfactants (e.g., sodium dodecyl sulfate (SDS)). We also demonstrate that the surfactant tolerance is related to the limited binding of SDS to the main-chain of the P(DEGMA- co -HPMA) macro-CTA constituting the particle shell. This work provides new insight into the interactions between surfactants and thermoresponsive copolymers and expands the scope of RAFT emulsion polymerization techniques for the preparation of noncrosslinked and surfactant-tolerant nanomaterials.