Design a Highly Reactive Trifunctional Core Molecule To Obtain Hyperbranched Polymers with over a Million Molecular Weight in One-Pot Click Polymerization

We present the first one-pot one-batch synthesis of hyperbranched polymers with over a million molecular weight and low polydispersity in the copper-catalyzed alkyne–azide cycloaddition (CuAAC) polymerization of AB 2 monomer. In contrast to the traditional triazido core molecule that failed to produce high molecular weight polymer, a novel tris-triazoleamine-based B 3 molecule was designed, which complexed with Cu I catalyst and activated the azido reactivity in both B 3 and B 3 -containing polymers. The polymerization demonstrated linear increase of polymer molecular weights with the feed ratio of [AB 2 ] 0:[B 3 ] 0 with no need of slow monomer addition. At the same time, a higher ratio of [Cu I ] 0:[B 3 ] 0 showed no influence on molecular weight but significantly increased the polymerization rate and produced hyperbranched polymers with higher degree of branching. The one-pot polymerization using [AB 2 ] 0:[B 3 ] 0:[Cu] 0 = 2700:1:10 produced hyperbranched polymers with molecular weight M n = 1.01 × 10 6 and polydispersity M w / M n = 1.05 in 4 h.