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

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journal contribution
posted on 09.02.2016, 00:00 by Xiaosong Cao, Yi Shi, Xiaofeng Wang, Robert W. Graff, Haifeng Gao
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 AB2 monomer. In contrast to the traditional triazido core molecule that failed to produce high molecular weight polymer, a novel tris-triazoleamine-based B3 molecule was designed, which complexed with CuI catalyst and activated the azido reactivity in both B3 and B3-containing polymers. The polymerization demonstrated linear increase of polymer molecular weights with the feed ratio of [AB2]0:[B3]0 with no need of slow monomer addition. At the same time, a higher ratio of [CuI]0:[B3]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 [AB2]0:[B3]0:[Cu]0 = 2700:1:10 produced hyperbranched polymers with molecular weight Mn = 1.01 × 106 and polydispersity Mw/Mn = 1.05 in 4 h.