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Influence of amorphous block on the thermal behavior of well-defined block copolymers based on ε-caprolactone

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Abstract

In this work, we studied the thermal characterization of block copolymers based on ε-caprolactone. The copolymers were obtained by anionic polymerization techniques, using different co-monomers such as styrene (S) and dimethylsiloxane (DMS). Synthesized copolymers were characterized by H-nuclear magnetic resonance, size exclusion chromatography, and Fourier transform infrared spectroscopy. Isothermal crystallization was performed by differential scanning calorimetry (DSC), and Avrami’s theory was employed in order to obtain kinetics parameters of interest, such as the half-life for the crystallization process (t 1/2), the bulk crystallization constant (k), and the Avrami’s exponent (n). The spherulitic growth was measured by polarized optical microscopy in order to determine the crystallization behavior. Poly(ε-caprolactone) block (PCL) crystallization was analyzed by considering the physico-chemical characteristics of the neighboring block, PS or PDMS. The chemical nature of the neighbor block in the PCL-based copolymer affects the kinetics parameters of Avrami’s equation, as can be deduced by comparing the values obtained for pure PCL and the studied block copolymers. On the other hand, the apparent thermal degradation activation energies E ad for PCL and block copolymers were determined by Ozawa’s method. The incorporation of PDMS instead of PS improves the stability of the resulting copolymer, as it was observed by thermogravimetric analysis.

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Acknowledgements

We express our gratitude to the Consejo Nacional de Investigaciones Científicas y Técnicas de la República Argentina (CONICET), the Agencia Nacional de Promoción Científica y Tecnológica (ANPCyT), and the Universidad Nacional del Sur (UNS, Argentina) for their financial support for this study.

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  1. Planta Piloto de Ingeniería Química (PLAPIQUI), Departamento de Ingeniería Química, Universidad Nacional del Sur (UNS), Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Camino “La Carrindanga” Km 7, 8000, Bahía Blanca, Argentina

    Mario D. Ninago, Angel J. Satti, Andrés E. Ciolino & Marcelo A. Villar

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  1. Mario D. Ninago
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Correspondence to Mario D. Ninago.

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Ninago, M.D., Satti, A.J., Ciolino, A.E. et al. Influence of amorphous block on the thermal behavior of well-defined block copolymers based on ε-caprolactone. J Therm Anal Calorim 112, 1277–1287 (2013). https://doi.org/10.1007/s10973-012-2673-z

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