Building copolymers with strict sequence control has been difficult to accomplish due to the order of monomer addition being solely governed by the relative rates of polymerization. One way of obtaining polymers with perfectly controlled sequences is to first use copper-catalyzed atom transfer radical addition (ATRA) to build alkyne-terminated "monomers.” Sequential ATRA reactions were performed with propargyl 2-bromoisobutryate (PBiB) and various acrylates, such as methyl, ethyl, and tetrahydrofurfuryl acrylate, using 1 mole percent of catalyst and achieving nearly quantitative conversions with photo-initiated methods after 12 h. The halogen moiety was converted to an azide, and CuAAC was used to perform an ARB-type step-growth polymerization. The overall reaction sequence is detailed in Scheme 1. Furthermore, this methodology was extended to larger polymer units synthesized by ATRP. Reaction conditions were optimized for temperature, catalyst regeneration method, concentration of monomer, and duration. Polymers were analyzed by <sup>1</sup>H NMR spectroscopy, MALDI-TOF, and Q-TOF mass spectroscopy.

ARB-type step-growth polymerization using CuAAC (copper catalyzed azide-alkyne cycloaddition) with sequence-controlled monomers synthesized by atom transfer radical addition (ATRA) and polymerization (ATRP)

254th National Meeting (2017)

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