A novel approach is presented for the synthesis of block-copolymers that resemble the architecture of a core cross-linked micelle. The polymers are synthesized from a combination of catalytic chain transfer polymerization (CCTP), thiol-Michael addition chemistry and reductive amination. A hydrophobic hyperbranched core is synthesized via CCTP of methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDMA), which affords control over the polymer architecture and the degree of chain end-functionality. The vinyl unsaturations of the hyperbranched polymers are converted in nucleophilic pendant amines by thiol-Michael addition using cysteamine hydrochloride. A polysaccharide shell is grafted onto the hyperbranched core via reductive amination with dextran (DEX). The synthesized poly(MMA-co-EGDMA)-b-DEX polymers possess an amphiphilic character, are colloidally stable and resemble the topology of a core cross-linked micelle. The presented methodology provides a robust, modular, and tuneable approach towards the synthesis of amphiphilic core cross-linked micelle analogues.
