Novel Polyesteramide-Based Diblock Copolymers: Synthesis by Ring-Opening Copolymerization and Characterization

✍ Scribed by Gaëlle Deshayes; Cécile Delcourt; Ingrid Verbruggen; Lise Trouillet-Fonti; Franck Touraud; Etienne Fleury; Philippe Degée; Mathias Destarac; Rudolph Willem; Philippe Dubois

• Publisher: John Wiley and Sons
• Year: 2009
• Tongue: English
• Weight: 358 KB
• Volume: 210
• Category: Article
• ISSN: 1022-1352
• DOI: 10.1002/macp.200900065

✦ Synopsis

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‐NH~2~ copoly[(ethylene oxide)‐co‐(propylene oxide)] copolymer [P(EO‐co‐PO)‐NH~2~]. 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 ^13^C 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)‐NH~2~]~0~ initial molar ratios.