Resorcinarene-based ATRP initiators for star polymers

Two novel multifunctional initiators for atom transfer radical polymeriza- tion (ATRP) were synthesized by derivatization of tetraethylresorcinarene. The deri- vatization induced a change in the conformation of the resorcinarene ring, which was confirmed by NMR spectroscopy. The initiators were used in ATRP of tert-butyl acrylate and methyl methacrylate, producing star polymers with controlled molar masses and low polydispersities. Instead of the expected star polymers with eight arms, polymers with four arms were obtained. Conformational studies on the initiators by rotating- frame nuclear Overhauser and exchange spectroscopy NMR and molecular modeling suggested that of eight initiator fun…