Novel Polyesteramide‐Based Diblock Copolymers: Synthesis by Ring‐Opening Copolymerization and Characterization |
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| Authors: | Gaë lle Deshayes,C cile Delcourt,Ingrid Verbruggen,Lise Trouillet‐Fonti,Franck Touraud,Etienne Fleury,Philippe Deg e,Mathias Destarac,Rudolph Willem,Philippe Dubois |
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| Affiliation: | 1. Center of Innovation and Research in Materials and Polymers (CIRMAP), Laboratory of Polymeric and Composite Materials, University of Mons‐Hainaut, Place du Parc 20, B‐7000 Mons, Belgium;2. High Resolution NMR Centre (HNMR), Department of Materials and Chemistry (MACH), Vrije Universiteit Brussel, Pleinlaan 2, B‐1050 Brussels, Belgium;3. Rhodia Recherche et Technologies, 85 Avenue des Frères Perret, F‐69192 Saint Fons, France |
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| Abstract: | Block copolymers based on a polyesteramide sequence and a polyether block were synthesized in bulk at 250 °C by ring‐opening copolymerization (ROP) of ε‐caprolactone (CLo) and ε‐caprolactam (CLa) as initiated by Jeffamine® M1000, i.e., ω‐NH2 copoly[(ethylene oxide)‐co‐(propylene oxide)] copolymer [P(EO‐co‐PO)‐NH2]. For an initial molar ratio of [CLa]0/[CLo]0 = 1, the copolymerization allowed for the formation of a diblock copolymer with a statistical polyesteramide sequence, as evidenced by 13C NMR. Investigation of the ROP mechanism highlighted that CLo was first polymerized, leading to the formation of a diblock copolymer P(EO‐co‐PO)‐b‐PCLo‐OH, followed by CLa hydrolysis to aminocaproic acid that inserted into the ester bonds of PCLo via aminolysis and subsequent condensation reactions. The outcome is the selective formation of P(EO‐co‐PO)‐b‐P(CLa‐co‐CLo)‐OH diblock copolymers where the composition and length of the polyesteramide sequence can be fine‐tuned by the [CLa]0/[CLo]0 and ([CLa]0 + [CLo]0)/[P(EO‐co‐PO)‐NH2]0 initial molar ratios. |
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| Keywords: | block copolymer ε ‐caprolactam ε ‐caprolactone polyesteramide ring‐opening polymerization |
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