Preparation of High-Density Polymer Brushes with a Multihelical Structure.

It is well-known that a mixture of isotactic and syndiotactic polymethyl methacrylate (PMMA) forms a stereocomplex consisting of a multihelical structure in which an isotactic chain is surrounded by a syndiotactic chain. Here, we report the basic structure of the stereocomplex formed when the syndiotactic PMMA chains are tethered to a silicon substrate and form a high-density polymer brush. The influence of geometric confinement was investigated by preparing the high-density polymer brushes on a flat and spherical substrate. In both cases, mixing the untethered isotactic PMMA with the grafted syndiotactic PMMA led to the formation of a stereocomplex with a multihelical structure. Static contact angle measurements showed a hindered surface mobility at the outermost surface of the polymer brush, indicating that the stereocomplex forms a crystalline structure. A syndiotactic polymer brush with substituted fluoroalkyl groups was prepared to increase the contrast for grazing incidence wide-angle X-ray diffraction (GIWAXD) measurements. The GIWAXD results verified that the stereocomplex forms a crystalline structure oriented perpendicular to the substrate with a relatively low degree of orientation.