Synthesis of high‐molecular‐weight cyclic and multicyclic polystyrenes

Different cyclic architectures were prepared by combination of living anionic polymerization and coupling reactions. Well‐defined macrocyclic polystyrenes were obtained by reaction of a two‐ended living precursor dianion with an electrophile compound. Two types of coupling agent (diethylenic and dihalogeno compounds) were used and their influence on the cyclization yield was studied. Cyclization with a diethylenic product is preferred as it generates a macrocycle with two living centers and is able to react with a (multifunctional) nucleophile leading to more complex architecture. Cyclic polystyrenes with two attached linear branches were obtained by consecutive coupling of monofunctional and difunctional living chains with DDPE (1,3‐bis(phenyl‐ethylenyl)benzene). High molar mass multicyclic polystyrene was prepared by reaction of living macrocycles with poly(chloromethylstyrene). Size exclusion chromatography and matrix‐assisted laser desorption ionization time of flight (MALDI‐TOF) mass spectrometry analyses have confirmed the high efficiency of these coupling reactions.