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Novel Polyesteramide‐Based Diblock Copolymers: Synthesis by Ring‐Opening Copolymerization and Characterization
Author(s) -
Deshayes Gaëlle,
Delcourt Cécile,
Verbruggen Ingrid,
TrouilletFonti Lise,
Touraud Franck,
Fleury Etienne,
Degée Philippe,
Destarac Mathias,
Willem Rudolph,
Dubois Philippe
Publication year - 2009
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.200900065
Subject(s) - copolymer , polymer chemistry , aminolysis , ethylene oxide , chemistry , ring opening polymerization , polymerization , materials science , polymer , organic chemistry , catalysis
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.