[en] The ring-opening polymerization and copolymerization of ε-caprolactone, ε-methyl-ε-caprolactone, β,δ-methyl-ε-caprolactone (mixed isomers), and L-lactide using aluminum isopropoxide as initiator were investigated. The chain propagation proceeds through a living anionic type coordinated insertion mechanism. The kinetic features of this process are reported. The experimental monomer reactivity ratios indicate that ε-caprolactone and its methyl derivatives yield random copolyesters. However, the ε-caprolactone/L-lactide pair exhibits a departure from randomness with the preferred incorporation of L-lactide units. The thermal properties of the copolymers were investigated by differential scanning calorimetry. It was found that the crystallization of ε-caprolactone units is limited, in all cases, to copolymers which are rich in this sort of unit. At the same time, the crystallization of L-lactide units was observed in copolymers with high concentrations of this comonomer. Analysis of the melting point depreasion data of the copolymers indicates that the L-lactide units are almost completely rejected from the caprolactone crystals, whereas about 50% of the ε-methyl-ε-caprolactone
and δ,δ-methyl-ε-caprolactone comonomer units are incorporated into the ε-caprolactone crystals due to an obvious structural similarity. Finally, poly(ε-caprolactone-co-ε-methyl-ε-caprolactone) samples are miscible with poly(viny1 chloride) (PVC) whatever the composition of the copolymer and the composition of the blend, whereas poly(εt-caprolactone-co-L-lactide) samples are miscible with PVC uniquely for copolymer L-lactide contents equal to or smaller than 40 wt %. In all cases where miscibility was found, a negative thermodynamic interaction parameter was computed.
Research Center/Unit :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Chemistry Materials science & engineering
Author, co-author :
Vion, Jean-Marc; Université de Liège - ULiège > Department of Chemistry > Laboratory of Macromolecular Chemistry and Organic Catalysis
Jérôme, Robert ; Université de Liège - ULiège > Department of Chemistry > Laboratory of Macromolecular Chemistry and Organic Catalysis
Teyssié, Philippe ; Université de Liège - ULiège > Department of Chemistry > Laboratory of Macromolecular Chemistry and Organic Catalysis
Aubin, Madeleine; University of Laval, Quebec, Canada > Department of Chemistry > Groupe de Recherche sur les Macromolécules
Prud'homme, Robert E; University of Laval, Quebec, Canada > Department of Chemistry > Groupe de Recherche sur les Macromolécules
Language :
English
Title :
Synthesis, characterization, and miscibility of caprolactone random copolymers
Publication date :
July 1986
Journal title :
Macromolecules
ISSN :
0024-9297
eISSN :
1520-5835
Publisher :
American Chemical Society, Washington, United States - District of Columbia
BELSPO - Politique scientifique fédérale IRSIA - Institut pour l'Encouragement de la Recherche Scientifique dans l'Industrie et l'Agriculture NSERC - Natural Sciences and Engineering Research Council FWB - Fédération Wallonie-Bruxelles Province of Québec. Department of Education
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