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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• 作者：Xiaosong Cao ; Yi Shi ; Xiaofeng Wang ; Robert W. Graff ; Haifeng Gao
• 刊名：Macromolecules
• 出版年：2016
• 出版时间：February 9, 2016
• 年：2016
• 卷：49
• 期：3
• 页码：760-766
• 全文大小：469K
• ISSN：1520-5835

文摘

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 Cu^I 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 [Cu^I]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 M_n = 1.01 × 10⁶ and polydispersity M_w/M_n = 1.05 in 4 h.