Synthesis and characterisation of non-ionic AB-diblock nanoparticles prepared by RAFT dispersion polymerization with polymerization-induced self-assembly

The synthesis and characterisation of soft matter nanoparticles based on AB diblock copolymers of oligo(ethylene glycol) methyl ether methacrylate (OEGMA) with 3-phenylpropyl methacrylate (PPMA) is described. Reversible addition-fragmentation chain transfer dispersion polymerization formulations that result in polymerization-induced self-assembly (RAFTDP-PISA) in methanol were utilized to access a range of poly(OEGMA-b-PPMA) (p(OEGMA-b-PPMA)) nanoparticles with the sphere-to-worm-to-vesicle order-order transitions being readily observed with increasing average degree of polymerization ((X) over barn) of the pPPMA block for a fixed (X) over barn of 28 for the pOEGMA block. Similarly the effect of total copolymer concentration on the resulting nanoparticle morphology is also demonstrated whereby we highlight how tuning of worm micelle diameters can be accomplished simply by varying the concentration of a formulation. The block copolymer nanoparticles were characterized by size exclusion chromatography (SEC), H-1 NMR spectroscopy, transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS). Additionally, we report the first examples utilizing 3D electron tomography and in situ atomic force microscopy (AFM) in methanol as convenient and powerful complementary techniques for the characterization of the resulting soft matter nano-objects with an emphasis on the direct visualization of worm nanoparticles.