One-Step Synthesis of Amphiphilic Ultrahigh Molecular Weight Block Copolymers by Surfactant-Free Heterogeneous Radical Polymerization

Ultrahigh molecular weight (>10 6 g/mol) amphiphilic block copolymers were synthesized using one-step surfactant-free heterogeneous radical polymerization (SFHRP). The polymerization initially involves formation of water-soluble homopolymer blocks, followed by copolymerization of a hydrophobic monomer, resulting in ultrahigh molecular weight block copolymers. Facilitating heterogeneous reaction conditions and continuous supply of an initiator controls the process. Using this synthetic approach, we synthesized amphiphilic block copolymers of poly(2-( N, N -dimethylamino)ethyl methacrylate)- block -poly( n -butyl acrylate) (pDMAEMA- b -pnBA), pDMAEMA- block -p( tert -butyl acrylate) (pDMAEMA- b -tBA), and pDMAEMA- block -polystyrene (pDMAEMA- b -pSt) with molecular weights of 1.98 × 10 6, 1.18 × 10 6, and 0.91 × 10 6 g/mol, respectively. These ultrahigh molecular weight block copolymers can self-assemble in nonpolar solvents to form thermochromic inverse polymeric micelles as well as other shapes and exhibit many potential applications.