Preparation of nanoparticles of double‐hydrophilic PEO‐PHEMA block copolymers by AGET ATRP in inverse miniemulsion

Atom transfer radical polymerization with activators generated by electron transfer initiating/catalytic system (AGET ATRP) of 2‐hydroxyethyl methacrylate (HEMA) was carried out in inverse miniemulsion. Water‐soluble ascorbic acid as a reducing agent and mono‐ and difunctional poly(ethylene oxide)‐based bromoisobutyrate (PEO‐Br) as a macroinitiator were used in the presence of CuBr 2 / tris [(2‐pyridyl)methyl]amine (TPMA) and CuCl 2 /TPMA complexes. The use of poly(ethylene‐ co ‐butylene)‐ block ‐poly(ethylene oxide) as a polymer surfactant resulted in the formation of stable HEMA cyclohexane inverse dispersion and PHEMA colloidal particles. All polymerizations were well‐controlled, allowing for the preparation of well‐defined PEO‐PHEMA and PHEMA‐PEO‐PHEMA block copolymers with relatively high molecular weight (DP > 200) and narrow molecular weight distribution ( M w / M n < 1.3). These block copolymers self‐assembled to form micellar nanoparticles being 10–20 nm in diameter with uniform size distribution, and aggregation number of ∼10 confirmed by atomic force microscopy and transmission electron microscopy.