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

摘要

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 X 10(6) and polydispersity M-w/M-n = 1.05 in 4 h.