Alkyl α-Hydroxymethyl Acrylate Monomers for Aqueous Dispersion Polymerization-Induced Self-Assembly

Baylis-Hillman reaction was used to afford a series of four alkyl a-hydroxymethyl acrylates, methyl (MHMA), ethyl (EHMA), isopropyl (iPrHMA), and n-butyl (nBHMA) a-hydroxymethyl acrylate, with tunable water solubility. MHMA and EHMA with high water solubility were identified as suitable candidates for aqueous dispersion polymerization-induced self-assembly (PISA). PISA of EHMA and MHMA using poly(ethylene glycol) macromolecular chain transfer agents (PEG(45)-CTA and PEG(113)-CTA) was investigated under either thermal or photoinitiation at 40-70 degrees C. Photo-PISA at low temperatures provided both morphological transition and PEG(45)-PEHMA(x) block copolymers with narrow molecular weight distributions. iPrHMA with moderate water solubility was used for dispersion-emulsion polymerization with the formation of vesicles being observed.