Crystallization-Driven Co-Assembly of Micrometric Polymer Hybrid Single Crystals and Nanometric Crystalline Micelles

In the present work, crystallization-driven coassembly of micrometric polymer single crystals and nanometric block copolymer micelles was achieved. The hybrid single crystals are first formed by cocrystallization of polyethylene (PE) homopolymer and polyethylene-b-poly­(tert-butyl acrylate) (PE-b-PtBA) block copolymer (BCP) in DMF or DMF/o-xylene mixed solvent. The morphology of the obtained hybrid single crystals can be regulated via changing the solvent composition, crystallization temperature and mass ratio of BCP/homopolymer. Because of the difference in crystallization rate, the distribution of PE-b-PtBA BCP in the hybrid single crystals may be inhomogeneous, leading to a concave gradient surface structure. The hybrid single crystals have a double-layer structure, in which PE homopolymer chains adopt extended conformation and the PE blocks in PE-b-PtBA are probably once-folded. After the PE homopolymer is consumed, cylindrical micelles of PE-b-PtBA can further epitaxially grow on the lateral surface of the hybrid single crystals and “ciliate paramecium-like” coassemblies are yielded. The single crystal/micelles coassemblies can be prepared either by one-step method, in which PE and PE-b-PtBA are added together in a single step, or by two-step method, in which the hybrid single crystals are prepared in the first step and extra PE-b-PtBA is added in the second step to grow BCP micelles. This work provided a simple route to construct hierarchical assemblies composed of objects with different scales by using crystallization as the key driving force.