One of the major complications in studying cyclic and multicyclic polymers has been the synthetic difficulty in preparing cyclic polymers in reasonable purity.  A number of recent techniques, such as the use of electrostatic attraction for templating cyclic structures or the metathesis ring expansion polymerization of cyclic initiators have expanded the understanding of these macrocyclic macromolecules tremendously.  One simple, yet versatile approach, is the use of highly efficient coupling chemistries (e.g. copper catalyzed azide-alkyne �click� coupling) in concert with a dropwise addition to yield high purity cyclic polymer.  The most noteworthy aspect of this approach is the broad compatibility with a range of polymer backbones and side-chain functionalities.  As a result, note only has the technique been coupled with a range of polymerization chemistries (e.g. atom transfer radical polymerization,  reversible addition, fragmentation chain transfer polymerization, ring opening polymerization, as well as anionic and cationic polymerization), it has been used to prepare exotic and novel cyclic polymer structures, including cyclic block copolymers, dendronized cyclic polymers, cyclic-grafted linear polymers, and multicyclic �cage� polymers.  Each of these architectures has been is being studied to ascertain the effect of the cyclic architecture on their physical properties.

Exploring the versatility of click chemistry in making cyclic polymers

245th National Meeting (2013)

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