Synthesis and Applications of Compartmentalised Molecular Polymer Brushes

Abstract

Polymer science is rapidly advancing towards the precise construction of synthetic macromolecules of formidable complexity. Beyond the impressive advances in control over polymer composition and uniformity enabled by the living polymerisation revolution, the introduction of compartmentalisation within polymer architectures can elevate their functionality beyond that of their constituent parts, thus offering immense potential for the production of tailor-made nanomaterials. In this Minireview, we discuss synthetic routes to complex molecular brushes with discrete chemical compartments and highlight their potential in the development of advanced materials with applications in nanofabrication, optics and functional materials.

Self‐Assembly of Diblock Molecular Polymer Brushes in the Spherical Confinement of Nanoemulsion Droplets

“…Potential areas of application for internally structured particles are being actively investigated, including the incorporation of responsive features as well as capture and release properties . Our findings also inspire more sophisticated self‐assembly scenarios, such as assembling (polymer) Janus nanoparticles or (rod‐like) diblock MPBs with intrinsic stiffness . Similarly, high aspect ratio diblock MPBs may be used to considerably increase the periodicity of polymer domains, leading to increased spacing between the stacked (or even concentric) lamellae and, ultimately, to structural colors.…”

“…They consist of a polymer backbone that is grafted with polymer side chains – typically leading to a stretched conformation of side chains and backbone. As MPBs show minimized chain entanglement, they are being increasingly investigated for self‐assembly applications and their behavior at interfaces . In particular, diblock MPBs comprise already phase‐separated compartments of high molecular weight and different chemistry which renders such block‐ or Janus‐type MPBs into nanoscale building blocks suitable for assembly in solution and bulk.…”

Cationic Bottlebrush Polymers from Quaternary Ammonium Macromonomers by Grafting‐Through Ring‐Opening Metathesis Polymerization

“…Four strategies exist to synthesize bottlebrush polymers, grafting‐onto, grafting‐from, transfer‐to, and grafting through, each of which have advantages and shortcomings 19,20. The grafting‐onto approach, which involves coupling separately pre‐polymerized side chains and backbones, limits branch density 21–23.…”

Polynorbornene‐g‐poly(ethylene oxide) Through the Combination of ROMP and Nitroxide Radical Coupling Reactions

“…The development of living polymerization processes combined with click chemistry has allowed to prepare various well‐defined graft copolymers with enormous versatility in their end‐ or side‐groups . Graft copolymers offer the unique possibility of tailoring materials properties through their structures that can be modified, such as the nature of the polymer backbone and composition, and the grafting density . Such versatility expands their scope to new applications that are not attainable with linear polymers .…”