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Stereocomplex crystallization behavior and physical properties of polyesterurethane networks incorporating diglycerol-based enantiomeric 4-armed lactide oligomers and a 1,3-propanediol-based 2-armed rac-lactide oligomer

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Abstract

The reactions of diglycerol-based 4-armed enantiomeric lactide oligomers (DG4LLAO and DG4DLAO, DGDLAO/DGLLAO = 1/1) and a 1,3-propanediol-based 2-armed rac-lactide oligomer (PD2racLAO) with hexamethylene diisocyanate produced bio-based polyesterurethane networks (PEU-DG4scLAO/PD2racLAOs) with different feed ratios of stereocomplex (sc) lactide oligomer (DG4scLAO = DG4DLAO + DG4LLAO) and PD2racLAO. Crystallization behavior and physical properties of PEU-DG4scLAO/PD2racLAOs were compared with those of the corresponding pentaerythritol- and glycerol-based polyesterurethane networks (PEU-PE4scLAO and PEU-GC4scLAO) with no PD2racLAO fraction. The X-ray diffraction analysis revealed that sc crystallites were formed without any homo-crystallization for PEU-DG4scLAO/PD2racLAOs 100/0-25/75 in a similar manner to PEU-PE4scLAO or PEU-GC3scLAO. Differential scanning calorimetric analysis for PEU-DG4scLAO/PD2racLAOs 100/0-25/75 revealed that the sc crystallites were not regenerated during a cold crystallization process of the quenched samples, but regenerated by isothermal crystallization from the melt. This result was a marked contrast to the previous result that sc crystallites were almost completely regenerated by the cold crystallization for PEU-PE4scLAO and PEU-GC3scLAO. Polarized optical microscopic analysis revealed that the incorporation of 25% of PD2racLAO enhanced the sc-nucleation efficiency, and further addition caused the reduction of overall crystallization. PEU-DG4scLAO/PD2racLAO 100/0 exhibited a higher elongation at break and tensile toughness than PEU-PE4scLAO and PEU-GC3scLAO. Tensile strength and elongation at break for PEU-DG4scLAO/PD2racLAOs decreased with increasing feed of PD2racLAO.

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Acknowledgements

We thank Dr. Naozumi Teramoto and Dr. Toshiaki Shimasaki of our department for their helpful suggestions. We are also grateful to Mr. Ryusuke Osada of the Material Analysis Center at the Chiba Institute of Technology for assisting in the XRD analysis reported here.

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Authors and Affiliations

  1. Department of Life and Environmental Sciences, Faculty of Engineering, Chiba Institute of Technology, 2-17-1, Tsudanuma, Narashino, Chiba, 275-0016, Japan

    Ayaka Shibita, Yuta Mizumura & Mitsuhiro Shibata

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  1. Ayaka Shibita
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  2. Yuta Mizumura
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  3. Mitsuhiro Shibata
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Correspondence to Mitsuhiro Shibata.

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Shibita, A., Mizumura, Y. & Shibata, M. Stereocomplex crystallization behavior and physical properties of polyesterurethane networks incorporating diglycerol-based enantiomeric 4-armed lactide oligomers and a 1,3-propanediol-based 2-armed rac-lactide oligomer. Polym. Bull. 74, 3139–3160 (2017). https://doi.org/10.1007/s00289-016-1890-1

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