Synthesis, Characterization, and Self-Assembly Behavior of Block Copolymers of N-Vinyl Pyrrolidone with n-Alkyl Methacrylates

Novel amphiphilic block copolymers of N-vinyl pyrrolidone (NVP) and either n-hexyl methacrylate (HMA, PNVP-<i>b</i>-PHMA) or stearyl methacrylate (SMA, PNVP-<i>b</i>-PSMA) were prepared by RAFT polymerization techniques and the sequential addition of monomers starting from the polymerization of NVP and using two different Chain Transfer Agents, CTAs. PNVP-<i>b</i>-PHMA are amorphous block copolymers containing constituent blocks with both high and low Tg values, whereas PNVP-<i>b</i>-PSMA are amorphous-semi-crystalline copolymers. Samples with different molecular weights and compositions were obtained. The copolymers were microphase-separated, but partial mixing was also observed. The presence of the amorphous PNVP block reduced the crystallinity of the PSMA blocks in the PNVP-<i>b</i>-PSMA copolymers. The thermal stability of the blocks was influenced by both constituents. The self-assembly behavior in THF, which is a selective solvent for polymethacrylate blocks, and in aqueous solutions, where PNVP was soluble, was examined. Unimolecular or low-aggregation-number micelles were obtained in THF for both types of samples. On the contrary, high-aggregation-number, spherical, and compact micelles were revealed in aqueous solutions. The increase in the steric hindrance of the side ester group of the polymethacrylate chain led to slightly lower degrees of association. The hydrophobic compound curcumin was efficiently encapsulated within the micellar core of the supramolecular structures in aqueous solutions. Micelles with higher aggregation numbers were more efficient in the encapsulation of curcumin. The results of this study were compared with those obtained from other block copolymers based on PNVP.