Abstract
A general method for the arm-first synthesis of star polymers through a formal A2 + B3 step-growth process is introduced. The synthesis relies on copper-catalyzed azide-alkyne cycloaddition (CuAAC) of N3-C(CR2)C-N3 macromonomers with a trifunctional alkyne crosslinker, and is enabled by the special mode of reactivity of 1,3-diazides in CuAAC. A variety of synthetic conditions were systematically evaluated, and effects of macromonomer size and feed ratio on the product structures have been investigated. Due to functional group tolerance of CuAAC, the presented methodology has a broad scope and can be extended to other macromonomers.
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