The Cu(0)-mediated reversible deactivation radical polymerisation of N,N’-dimethylaminoethyl acrylate in DMSO and IPA at ambient temperature using Cu(0) wire is investigated. Tetra-functional and octa-functional initiators were utilised to facilitate the synthesis of well-defined PDMAEA star homo and block copolymers with a range of molecular weights (Mn ~ 5000-41000 g mol-1). Both solvents demonstrated to be excellent media for the controlled polymerisation of DMAEA yielding narrow molecular weight distributions (dispersity ~ 1.1) when the reactions were ceased at ~ 40% conversion. Interestingly, at high conversions (typically &gt; 55%) high and low molecular weight shoulders were evident by SEC when DMSO and IPA were used respectively, suggesting a large extent of termination and/or side reactions at prolonged reaction times. Nevertheless, high end group fidelity could be maintained when immediate precipitation of the polymers (at lower conversion) was performed yielding low dispersed P(DMAEA-b-MA) star block copolymers with molecular weights of around 20000 g mol-1 (dispersity typically less than 1.20). Importantly, guidelines on how to prevent hydrolysis, termination and side reactions of PDMAEA as well as how to purify and store such materials are also provided and discussed.

Well-defined PDMAEA stars via Cu(0)-mediated reversible deactivation radical polymerisation

253rd National Meeting (2017)

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