Soluble, branched vinyl copolymers with very high molecular weight may be readily synthesised using controlled radical polymerisations and low molar concentrations of multi-vinyl comonomers (less than one per primary chain). The avoidance of gelation is achieved simply by empirical experimentation but highly reproducible syntheses result, and the matching of experiment with theory is observed when considering initiation efficiencies. The conjoined chains are bound together at high conversion (typically &gt;80%), opening a new strategy for controlling functionality through the use of mixed initiator feedstocks – a conventionally pointless approach to enabling functional material samples. Through the design and selection of oligomeric, dendritic, functional, hydrophilic, hydrophobic and carbohydrate initiators high molecular weight branched copolymer architectures have been formed with controlled ratios of different functional groups. When selecting water-soluble vinyl monomers, highly efficient surfactants have been generated that allow the formation of remarkably stable macro and nano emulsions. In contrast, hydrophobic monomers allow the branched architectures to maintain amphiphilic character, enabling the controlled formation of highly uniform nanoparticles with controlled surface functionality, including surface patches, after facile nanoprecipitation.<br/>Within this report, the use of mixed initiation in branched vinyl copolymers will be presented with examples showing how a variety of mixed chain-end functionalities can be readily achieved, leading to controlled behaviour, nanoparticle formation and influence of the physical properties of the resulting materials.

Mixed initiation as a strategy for controlling surface functionality within branched vinyl copolymer-derived nanoparticles

256th National Meeting (2018)

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