Stars and dendrimer‐like architectures by the divergent method using controlled radical polymerization

Using novel multihalide compounds based on 4‐tert‐butylcalix4,6,8]arenes as initiators, molecularly well‐defined polystyrenes (PS) and polyalkyl‐(meth)acrylates] could be obtained by atom transfer radical polymerization (ATRP). This core‐first approach and therefore the very same initiators also served to derive star block copolymers. Dendrimer‐like architectures based on poly(ethylene oxide) (PEO) and PS were prepared upon combination of anionic polymerization for the inner PEO part and ATRP for the outer PS shell.