Kinetic study of copper(I)‐catalyzed click chemistry step‐growth polymerization |
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Authors: | Sandra Binauld Fernande Boisson Thierry Hamaide Jean‐Pierre Pascault Eric Drockenmuller Etienne Fleury |
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Affiliation: | 1. Université de Lyon, Lyon, F‐69003, France;2. INSA de Lyon, IMP/LMM Laboratoire des Matériaux Macromoléculaires, CNRS UMR 5223, Ingénierie des Matériaux Polymères, Villeurbanne, F‐69621, France;3. Université Lyon 1, IMP/LMPB Laboratoire des Matériaux Polymères et Biomatériaux, CNRS UMR 5223, Ingénierie des Matériaux Polymères, Villeurbanne, F‐69621, France;4. Service de RMN, Réseau des Polyméristes Lyonnais (IMP, UMR CNRS 5223), BP 24, 69390 Vernaison, France |
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Abstract: | Oligomers and polymers containing triazole units were synthesized by the copper(I)‐catalyzed 1,3‐dipolar cycloaddition step‐growth polymerization of four difunctional azides and alkynes. In a first part, monofunctional benzyl azide was used as a chain terminator for the polyaddition of 1,6‐diazidohexane and α,ω‐bis(O‐propargyl)diethylene glycol, leading to polytriazole oligomers of controlled average degree of polymerization (DPn = 3–20), to perform kinetic studies on low‐viscosity compounds. The monitoring of the step‐growth click polymerization by 1H NMR at 25, 45, and 60 °C allowed the determination of the activation energy of this click chemistry promoted polyaddition process, that is, Ea = 45 ± 5 kJ/mol. The influence of the catalyst content (0.1–5 mol % of Cu(PPh3)3Br according to azide or alkyne functionalities) was also examined for polymerization kinetics performed at 60 °C. In a second part, four high molar mass polytriazoles were synthesized from stoichiometric combinations of diazide and dialkyne monomers above with p‐xylylene diazide and α,ω‐bis(O‐propargyl)bisphenol A. The resulting polymers were characterized by DSC, TGA, SEC, and 1H NMR. Solubility and thermal properties of the resulting polytriazoles were discussed based on the monomers chemical structure and thermal analyses. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5506–5517, 2008 |
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Keywords: | catalysts kinetics step‐growth polymerization thermal properties |
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