Role of Competitive Crystallization Kinetics in the Formation of 2D Platelets with Distinct Coronal Surface Patterns via Seeded Growth

Low dispersity 2D platelet micelles with controllable surface patterns were prepared by seeded-growth/living crystallization driven self-assembly (CDSA) of block copolymer/homopolymer (BCP/HP) blends of poly(ferrocenyldimethylsilane)-b-poly(2-vinyl pyridine) (PFS-b-P2VP) and PFS. The precise morphology was found to be dependent on the proportion of the P2VP corona block, which can be efficiently controlled by changing the molar concentration ratio of PFS-b-P2VP/PFS, (cB/cH)t, as well as their relative rates of crystallization, (GB/GH)t. In the case where their molar concentration ratio was comparable to their crystallization rate ratio, platelets with a uniform distribution of P2VP coronal chains were formed. In other cases, as the concentration ratio increased (or decreased) during the living CDSA process, hierarchical structures were formed, including chain-like assemblies consisting of end-to end linked rectangular platelets and fusiform (tapered) micelles. (GB/GH)t was adjusted by tuning the degree of polymerization of the crystallizable PFS core-forming block and the BCP block ratio and by varying the terminus of the HP or changing the solvent used. Furthermore, the open edge of the platelets remained active for further growth, which permitted control of the morphology and dimensions of the platelets. Interestingly, in cases where the molar concentration ratio was lower than the crystallization rate ratio, growth rings were observed after two or more living CDSA steps. This study on the formation of platelet micelles by living CDSA of BCP/HP blends under kinetic control offers a considerable scope for the design of 2D polymer nanomaterials with controlled shape and surface patterns.