Toward self-assembling dendritic macromolecules from conventional monomers by a combination of living radical polymerization and irreversible terminator multifunctional initiator

TERMINI stands for irreversible terminator multifunctional initiator and represents a new concept elaborated in our laboratory for the design of novel macromolecules with complex architecture from a diversity of commercial monomers. TERMINI is a masked multifunctional initiator that quantitatively interrupts a living polymerization. After demasking, the TERMINI-derived repeat unit provides access to a quantitative reinitiation of the same living polymerization in more than one direction, thus becoming a branching point. In this article, with a combination of self-regulated metal-catalyzed living radical polymerization and TERMINI, we demonstrate a new method for the divergent synthesis of dendritic poly(methyl methacrylate) containing a bifunctional core at its focal point. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 505–513, 2004