Macromolecules with complex architectures such as molecular brushes (MBs) have received much attention over the last two decades. This interest is largely due to their potential applications in many fields, such as drug delivery and electronics, among others. The synthesis of such complex macromolecules can only be achieved via the use of controlled polymerization techniques such as atom transfer radical polymerization (ATRP). This review highlights the use of ATRP in the synthesis of MBs.

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We report the synthesis of amphiphilic hetero-arm molecular brushes (AMBs), which were prepared by a combination of ‘grafting from’ and ‘grafting onto’ methodologies. First, styrene-terminated polyethylene glycol macromonomer (VB-PEG12, ∼666 g mol–1) was copolymerized with maleic anhydride (MAnh) to yield a polymer containing hydrophilic PEG chains and reactive (MAnh) groups. Subsequently, the reactive MAnh units in the obtained polymer were modified via a ring-opening reaction using primary alkyl amines, with different alkyl chain lengths, as the nucleophile. In situ ring closure yielded the styrene–maleimide-based AMB. The amphiphilic character of the AMBs was used for their self-assembly in different solvents. The effect of the ratio in hydrophilic to hydrophobic graft length on the morphology of the assemblies was studied using scanning electron microscopy.

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