TY - JOUR
T1 - Activation of the hydrolytic polymerization of ε-caprolactam by ester functions
T2 - Straightforward route to aliphatic polyesteramides
AU - Deshayes, Gaëlle
AU - Delcourt, Cécile
AU - Verbruggen, Ingrid
AU - Trouillet-Fonti, Lise
AU - Touraud, Franck
AU - Fleury, Etienne
AU - Degée, Philippe
AU - Destarac, Mathias
AU - Willem, Rudolph
AU - Dubois, Philippe
PY - 2008/9/1
Y1 - 2008/9/1
N2 - The hydrolytic polymerization of ε-caprolactam (CLa) was carried out in bulk (in absence of solvent) at 250 °C in the presence of carboxylic esters and aqueous H3PO2. It turned out that by conducting the ring opening polymerization (ROP) of CLa in the presence of PEO-C(O)-O-C5H11, a selected model ester (PEO = poly(ethylene oxide)), a remarkable activating effect of the ester function on the hydrolytic polymerization of the lactam was observed yielding PEO-b-PCLa diblock copolymers. The comparison of the CLa monomer conversions obtained with or without the model ester activated by H3PO2, as determined by 1H NMR spectroscopy, has enabled to propose a multi-step mechanism in which three major reactions occurred: (i) ester and lactam hydrolysis, (ii) aminolysis of the carboxylic ester by the resulting primary amine of the hydrolyzed/opened lactam ring and (iii) condensation reactions between carboxylic acids and both amine/hydroxyl functions. The overall result of this multi-step mechanism can be assimilated as an "insertion" of the opened lactam into the ester function. By conducting the hydrolytic polymerization of CLa in the presence of an aliphatic polyester chain, such as poly(ε-caprolactone) (PCLo), polyesteramides were recovered with high yields and random distributions of the CLa and CLo repetitive units as determined by 13C NMR.
AB - The hydrolytic polymerization of ε-caprolactam (CLa) was carried out in bulk (in absence of solvent) at 250 °C in the presence of carboxylic esters and aqueous H3PO2. It turned out that by conducting the ring opening polymerization (ROP) of CLa in the presence of PEO-C(O)-O-C5H11, a selected model ester (PEO = poly(ethylene oxide)), a remarkable activating effect of the ester function on the hydrolytic polymerization of the lactam was observed yielding PEO-b-PCLa diblock copolymers. The comparison of the CLa monomer conversions obtained with or without the model ester activated by H3PO2, as determined by 1H NMR spectroscopy, has enabled to propose a multi-step mechanism in which three major reactions occurred: (i) ester and lactam hydrolysis, (ii) aminolysis of the carboxylic ester by the resulting primary amine of the hydrolyzed/opened lactam ring and (iii) condensation reactions between carboxylic acids and both amine/hydroxyl functions. The overall result of this multi-step mechanism can be assimilated as an "insertion" of the opened lactam into the ester function. By conducting the hydrolytic polymerization of CLa in the presence of an aliphatic polyester chain, such as poly(ε-caprolactone) (PCLo), polyesteramides were recovered with high yields and random distributions of the CLa and CLo repetitive units as determined by 13C NMR.
KW - ε-Caprolactam
KW - Hydrolytic polymerization
KW - Polyamide
KW - Polyesteramides
KW - Ring-opening polymerization
UR - http://www.scopus.com/inward/record.url?scp=49549092472&partnerID=8YFLogxK
U2 - 10.1016/j.reactfunctpolym.2008.06.020
DO - 10.1016/j.reactfunctpolym.2008.06.020
M3 - Article
AN - SCOPUS:49549092472
SN - 1381-5148
VL - 68
SP - 1392
EP - 1407
JO - Reactive and Functional Polymers
JF - Reactive and Functional Polymers
IS - 9
ER -