Designing Multicyclic Polymer Topologies by Electrostatic Macromolecular Self-Assembly and Covalent Fixation

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A systematic classification of nonlinear polymer architectures is formulated by reference to constitutional isomerism in a series of alkanes (C_nH_<2n+2>), monocycloalkanes (C_nH_<2n>) and polycycloalkanes (C_nH<2n-2>, C_nH_<2n-4>, etc). And a variety of topologically unique polymers, such as monocyclic and polycyclic polymers, cyclic telechelics (kyklo-telechelics), cyclic macromonomers and polymeric topological isomers have been constructed by means of an "electrostatic self-assembly and covalent fixation" strategy. In this process, new telechelic polymer precursors having moderately strained cyclic onium salt groups carrying multifunctional carboxylate counteranions have been prepared as key polymer precursors. The unique electrostatic self assembly, formed particularly in a dilute solution, was covalently fixed through the ring-opening reaction by heating, to produce a variety of nonlinear polymer architectures in high efficiency.