Tailoring the Multicompartment Nanostructures of Fluoro-Containing ABC Triblock Terpolymer Assemblies via Polymerization-Induced Self-Assembly

Abstract

Polymer self-assembly has been one of the most important strategies for preparation of multicompartment micelles (MCMs). However, the traditional self-assembly techniques are constrained by limited common solvent, complex kinetic factors, low solids content, etc. Polymerization-induced self-assembly (PISA) is a novel technique for preparation of polymer assemblies at high solids content and has been exploited to produce MCMs. Nevertheless, the morphology evolution of the MCMs obtained through PISA has not yet been well understood. Herein, we study the compartmentalization behaviors of a series of MCMs constituted by poly­(N,N-dimethyl­aminoethyl methacrylate)-b-poly­(benzyl methacrylate)-b-poly­(2-perfluorohexylethyl methacrylate) (PDMA-b-PBzMA-b-PFHEMA) triblock terpolymers, which were synthesized by seeded reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization of FHEMA using PDMA-b-PBzMA micelles, wormlike micelles, or vesicles as the seeds. Because of the strong incompatibility between PBzMA and PFHEMA, MCMs with abundant compartmentalized nanostructures were produced. Phosphotungstic acid- and RuO4-stained TEM images of these MCMs indicate that their morphologies are controlled by both the DPs of PBzMA and PFHEMA. Our results suggest that PISA could serve as a reliable platform for revealing the compartmentalization behaviors of polymeric assemblies.

Semi‐Fluorinated Methacrylates: A Class of Versatile Monomers for Polymerization‐Induced Self‐Assembly

“…Besides, M n of these block copolymers increases with the monomer conversion, and the dispersities are <1.30 for all the copolymers (Figure c). However, because of the strong associative interactions among the fluoro‐containing blocks, the solubility of PFBEMA decreases with the chain length of PFBEMA, leading to an increscent deviation between the theoretical and the actual M n . DLS studies indicate that after 3 h of polymerization, aggregates of 15 nm formed.…”

“…Compared with the traditional self‐assembly protocols, PISA allows preparing the desired polymer assemblies via readily adjusting the polymer‐related parameters, including hydrophilic/hydrophobic ratio and polymer concentration. Hence, PISA has been extensively studied to understand the self‐assembly mechanism of amphiphilic copolymers and to develop new drug carriers, dynamic gels, Pickering emulsifiers, etc …”

Tunable Fluorophobic Effect Determines Nanoparticle Dispersion in Homopolymers and Block Polymers

“…Remarkably, the fluorophobic association of the tails resulted in the homopolymers behaving like a block polymer with lamellar‐like phase separation of the blocks . Fluorinated block polymers are also known to undergo strong phase separation owing to the high effective interaction parameter χ with nonfluorinated blocks, sometimes giving rise to unique morphologies such as multicompartment micelles with three distinct chemical phases …”

Photoinitiated Seeded RAFT Dispersion Polymerization: A Facile Method for the Preparation of Epoxy‐Functionalized Triblock Copolymer Nano‐Objects

“…Over the past decade, polymerization‐induced self‐assembly (PISA) of block copolymers via reversible addition–fragmentation chain transfer (RAFT)‐mediated dispersion polymerization has enabled block copolymer nano‐objects with a diverse set of complex morphologies to be synthesized at high solids content (up to 50%) . However, the RAFT‐mediated PISA is typically conducted at high temperatures (e.g., 70 C) by thermal initiation, which is not beneficial for the preparation of temperature sensitive polymer nano‐objects (e.g., protein–polymer conjugate).…”