ABC Triblock Copolymer Worms: Synthesis, Characterization, and Evaluation as Pickering Emulsifiers for Millimeter Sized Droplets
Polymerization induced self assembly (PISA) is used to prepare linear poly(glycerol monomethacrylate) poly(2 hydroxypropyl methacrylate) poly(benzyl methacrylate) [PGMA PHPMA PBzMA] triblock copolymer nano objects in the form of a concentrated aqueous dispersion via a three step synthesis based on reversible addition fragmentation chain transfer (RAFT) polymerization. First, GMA is polymerized via RAFT solution polymerization in ethanol, then HPMA is polymerized via RAFT aqueous solution polymerization, and finally BzMA is polymerized via "seeded" RAFT aqueous emulsion polymerization. For certain block compositions, highly anisotropic worm like particles are obtained, which are characterized by small angle X ray scattering (SAXS) and transmission electron microscopy (TEM) The design rules for accessing higher order morphologies (i.e. worms or vesicles) are briefly explored. Surprisingly, vesicular morphologies cannot be accessed by targeting longer PBzMA blocks instead, only spherical nanoparticles are formed. SAXS is used to rationalize these counterintuitive observations, which are best explained by considering subtle changes in the relative enthalpic incompatibilities between the three blocks during the growth of the PBzMA block. Finally, the PGMA PHPMA PBzMA worms are evaluated as Pickering emulsifiers for the stabilization of oil in water emulsions. Millimeter sized oil droplets can be obtained using low shear homogenization (hand shaking) in the presence of 20 vol n dodecane. In contrast, control experiments performed using PGMA PHPMA diblock copolymer worms indicate that these more delicate nanostructures do not survive even these mild conditions.
Macromolecules