Self-assembly and covalent fixation for topological polymer chemistry

A novel methodology (electrostatic self-assembly and covalent fixation) has been proposed for designing various nonlinear polymer topologies, includin g monocyclic and polycyclic polymers, cyclic macromonomers and cyclic telec helics (kyklo-telechelics), a-ring-with-a-branch topology polymers and poly meric topological isomers, as well as branched model polymers, such as star polymers and polymacromonomers. Thus, new telechelic polymer precursors ha ving a moderately strained cyclic onium salt group as single or multiple en d groups and carrying multifunctional carboxylates as the counterions were prepared through an ion-exchange reaction. A variety of electrostatic self- assemblies of these polymer precursors, formed particularly in dilute organ ic solution, was then subjected to heat in order to convert the ionic inter actions into covalent linkages by ring-opening reaction, and to produce top ologically unique, nonlinear polymer architectures in high efficiency.