pH-dependent micellization of poly(2-vinylpyridine)-block-poly((dimethylamino)ethyl methacrylate) diblock copolymers

A series of poly(2-vinylpyridine)-block-poly((dimethylamino)ethyl methacrylate) diblock copolymers (P2VP-b-PDMAEMA) have been synthesized by living anionic polymerization of the comonomers. Dynamic light scattering (DLS) has been used to study the associative behaviour of these copolymers in water as a function of copolymer composition, pH, ionic strength, and temperature. Three association regimes are observed. At low pH, loose aggregates are formed, although both the P2VP and PDMAEMA blocks are protonated. At intermediate pH, micelles are observed that consist of an uncharged hydrophobic P2VP core surrounded by a protonated PDMAEMA corona. At higher pH, the PDMAEMA corona is essentially uncharged and collapses at temperatures higher than 40 °C, which results in unstable micelles. The micelles observed by transmission electron microscopy are spherical.