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Crystallization of novel poly(ε-caprolactone)-block-poly(propylene adipate) copolymers

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Abstract

Poly(ε-caprolactone)-block-poly(propylene adipate) (PCL-block-PPAd) copolymers were prepared using a combination of polycondensation and ring opening polymerization of ε-CL. 1H-NMR and 13C-NMR spectroscopy showed that the prepared copolymers were block. Also, the copolymer composition was calculated from NMR spectra and was found similar to the feeding ratio. The copolymers formed PCL crystals as was proved by WAXD. The crystallization rates and degree of crystallinity, measured from DSC crystallization experiments, decreased with PPAd content. The equilibrium melting points of PCL were estimated applying the Hoffmann–Weeks method and the observed melting point depression was analyzed using the Nishi–Wang equation which showed that there is some miscibility of the copolymer segments. Isothermal crystallization experiments after self-nucleation were performed to distinguish the nucleation and crystal growth stages during isothermal crystallization. The secondary nucleation theory was then used and the obtained data for crystallization rates, estimated from the inverse of the crystallization half-times, were analyzed. The resulting values for nucleation constant K g, and also for the surface free energies and work of chain folding, increased with PPAd content due to topological restrictions.

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Authors and Affiliations

  1. Laboratory of Polymer Chemistry and Technology, Department of Chemistry, Aristotle University of Thessaloniki, 541 24, Thessaloniki, Macedonia, Greece

    Stavroula G. Nanaki, George Z. Papageorgiou & Dimitrios N. Bikiaris

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  1. Stavroula G. Nanaki
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  2. George Z. Papageorgiou
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  3. Dimitrios N. Bikiaris
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Correspondence to Dimitrios N. Bikiaris.

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Nanaki, S.G., Papageorgiou, G.Z. & Bikiaris, D.N. Crystallization of novel poly(ε-caprolactone)-block-poly(propylene adipate) copolymers. J Therm Anal Calorim 108, 633–645 (2012). https://doi.org/10.1007/s10973-011-2155-8

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