General pathway toward crystalline-core micelles with tunable morphology and corona segregation.

We present a general mechanism for the solution self-assembly of crystalline-core micelles (CCMs) from triblock copolymers bearing a semicrystalline polyethylene (PE) middle block. This approach enables the production of nanoparticles with tunable dimensions and surface structures. Depending on the quality of the solvent used for PE, either spherical or worm-like CCMs can be generated in an easy and highly selective fashion from the same triblock copolymers via crystallization-induced self-assembly upon cooling. If the triblock copolymer stays molecularly dissolved at temperatures above the crystallization temperature of the PE block, worm-like CCMs with high aspect ratios are formed by a nucleation and growth process. Their length can be conveniently controlled by varying the applied crystallization temperature. If exclusively spherical micelles with an amorphous PE core are present before crystallization, confined crystallization within the cores of the preformed micelles takes place and spherical CCMs are formed. For polystyrene-block-polyethylene-block-poly(methyl methacrylate) triblock terpolymers a patch-like microphase separation of the corona is obtained for both spherical and worm-like CCMs due to the incompatibility of the PS and PMMA blocks. The structure of the patch-like corona depends on the selectivity of the employed solvent for the PS and PMMA corona blocks, whereby nonselective solvents produce a more homogeneous patch size and distribution. Annealing of the semicrystalline PE cores results in an increasingly uniform crystallite size distribution and thus core thickness of the worm-like CCMs.