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Fractionated Crystallization Kinetics and Polymorphic Homocrystalline Structure of Poly(L-lactic acid)/Poly(D-lactic acid) Blends: Effect of Blend Ratio

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Abstract

Stereocomplex (SC) crystallization has been an effective way to improve the physical performances of stereoregular polymers. However, the competition between homo and SC crystallizations can lead to more complicated crystallization kinetics and polymorphic crystalline structure in stereocomplexable polymers, which influences the physical properties of obtained materials. Herein, we select the medium-molecular-weight (MMW) poly(L-lactic acid)/poly(D-lactic acid) (PLLA/PDLA) asymmetric blends with different PDLA fractions (fD=0.01–0.5) as the model system and investigate the effects of fD and crystallization temperature (Tc) on the crystallization kinetics and polymorphic crystalline structure. We observe the fractionated (i.e., multistep) crystallization kinetics and the formation of peculiar β-form homocrystals (HCs) in the asymmetric blends under quiescent conditions, which are strongly influenced by both fD and Tc. Precisely, crystallization of β-form HCs is favorable in the MMW PLLA/PDLA blends with high fD (≥0.2) at a low Tc (80–100 °C). It is proposed that the formation of metastable β-form HCs is attributed to the conformational matching between β-form HCs and SCs, and the stronger constrain effects of precedingly-formed SCs in the early stage of crystallization. Such effects can also cause the multistep crystallization kinetics of MMW PLLA/PDLA asymmetric blends in the heating process.

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Acknowledgments

This study was financially supported by the National Natural Science Foundation of China (No. 21873083). WAXD measurement were performed on the beamline BL16B1 of SSRF.

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Authors and Affiliations

  1. State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, 310027, China

    Wang-Kai Xiang, Qing Xie, Shan-Shan Xu, Chen-Xuan Sun, Cheng-Tao Yu, Ying Zheng & Peng-Ju Pan

  2. Institute of Zhejiang University-Quzhou, Quzhou, 324000, China

    Wang-Kai Xiang, Cheng-Tao Yu, Ying Zheng & Peng-Ju Pan

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  1. Wang-Kai Xiang
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  2. Qing Xie
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  6. Ying Zheng
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Correspondence to Ying Zheng or Peng-Ju Pan.

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Xiang, WK., Xie, Q., Xu, SS. et al. Fractionated Crystallization Kinetics and Polymorphic Homocrystalline Structure of Poly(L-lactic acid)/Poly(D-lactic acid) Blends: Effect of Blend Ratio. Chin J Polym Sci 40, 567–575 (2022). https://doi.org/10.1007/s10118-022-2658-8

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