Structure and Self-Assembly of Oligocarbonate-Fluorene End Functionalized Poly (ethylene glycol) ABA Triblock Polymer

Hierarchical structures of oligocarbonate-fluorene end-functionalized poly(ethylene glycol) triblock copolymer (P(F-TMC)m-PEG444-P(F-TMC)m) were characterized by light scattering, atomic force microscopy, and Ultraviolet-visible spectroscopy in dilute regime in water, a poor solvent of F-TMC block. The evidence for pai-pai stacked of F-TMC block in self-assembled structure was provided. The self-assembly behavior is highly dependent on concentration and F-TMC block length, m. The presence of clusters dominates the population of scatterers once m is larger than 2, where there is no clear evidence of a separation of micelles and clusters. The molecular aggregation driven by F-TMC groups appears too strong to permit labile micelle-cluster dynamics as observed with m $=$ 2 and 1.2. The non-mean field scaling of the aggregation number, when compared to models for triblock copolymers, highlights the need for a molecular-based model to predict the self-assembly at low end-group numbers. In our case, the end-groups are oligomers, so the comparison to Flory scaling may not be justified.