Thermo-Reversible Formation of Wormlike Micelles with a Microphase-Separated Corona from a Semicrystalline Triblock Terpolymer

The thermo-reversible formation of wormlike micelles from a polystyrene-block-polyethylene-block-poly(methyl methacrylate) (PS-b-PE-b-PMMA) triblock terpolymer with a crystallizable middle block in organic media is presented. The formation of wormlike micelles is rather unexpected, because PE containing diblock copolymers usually form platelet-like structures. Transmission electron microscopy (TEM) investigations revealed a core−corona structure for the wormlike micelles. The core is formed by crystalline PE domains, and the soluble corona exhibits a patched structure composed of microphase-separated PS and PMMA chains. Microphase separation of the coronal chains was proven by 2D ¹H nuclear Overhauser effect spectroscopy (NOESY) and TEM investigations of selectively stained samples. A combination of various techniques, such as differential scanning calorimetry (DSC), dynamic light scattering (DLS), and scanning force microscopy (SFM), indicated that the wormlike micelles might be formed by crystallization-induced aggregation of spherical micelles upon cooling. The presented approach opens an alternative way to produce anisotropic polymer nanostructures with a microphase-separated corona.