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Toward a Further Understanding of the Decreased β-Phase Content in β-Nucleated Polypropylene Random Copolymer: From Nucleation and Growth Kinetics

  • Xuan Sha
    Xuan Sha
    State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200433, P. R. China
    More by Xuan Sha
  • Yang Yue
    Yang Yue
    State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200433, P. R. China
    More by Yang Yue
  • Wenan Tie
    Wenan Tie
    Shaanxi Yanchang Jingwei New Material Technology Industrial Park Co., Ltd., Xi’an, Shaanxi 710054, P. R. China
    More by Wenan Tie
  • Xiaoyan Tian
    Xiaoyan Tian
    Shaanxi Yanchang Jingwei New Material Technology Industrial Park Co., Ltd., Xi’an, Shaanxi 710054, P. R. China
    More by Xiaoyan Tian
  • , and 
  • Jiachun Feng*
    Jiachun Feng
    State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200433, P. R. China
    *Email: [email protected]
    More by Jiachun Feng
Cite this: ACS Appl. Polym. Mater. 2023, 5, 9, 7507–7518
Publication Date (Web):August 26, 2023
https://doi.org/10.1021/acsapm.3c01407
Copyright © 2023 American Chemical Society

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    Abstract

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    Compared with polypropylene homopolymer (PPH), β-nucleating agent (β-NA) usually induces less β-phase in polypropylene random copolymer (PPR) with comonomer inserted. A widely held view is that unfavorable β-growth kinetically caused by the insertion of comonomer contributes to a decreased relative content of β-phase (kβ) in PPR. To further understand the decreased kβ in PPR, we separately investigated the nucleation and growth behavior of various isotactic polypropylenes (iPPs) nucleated with a β-NA, N,N′-dicyclohexylterephthalamide (DCHT). With the aid of fractionated crystallization, the possibility of DCHT to form β-nuclei, iβ/i, is calculated to be reduced in PPR with ethylene inserted, demonstrating fewer β-nuclei induced. As for growth, it is found that the insertion of comonomer decreases the relative growth rate of β-phase (Gβ/Gα) and weakens the kinetic advantage of β-growth. The study reveals that both iβ/i and Gβ/Gα decrease with the insertion of comonomer. Fewer β-nuclei induced by DCHT and the subsequent unfavorable β-growth simultaneously contribute to the final decreased kβ. Our fundamental insight provides a more comprehensive understanding of the decreased kβ as comonomer is inserted into the iPP chain and could have important implications in the control of the polymorphism of polymers.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsapm.3c01407.

    • 13C NMR spectra for iPP samples; SSA final melting curves and corresponding fitting peaks for iPP samples; SEM images and droplet size distribution of PS/iPP(DCHT) blends; DSC cooling and the subsequent heating curves for PS/iPP samples; enlarged view of cooling curves in the temperature range of 30–90 °C for PS/iPP(DCHT) samples; WAXS profiles of the PP phase for standard crystals of PS/iPP(DCHT) blends; POM images of iPP and iPP/CaPim; comparison of Gα and Gβ for iPPs; in situ WAXS profiles during the non-isothermal crystallization process for iPP/DCHT samples; the melting temperature and the corresponding normalized area of the fitted peaks for SSA curves; the morphological characterization of the prepared PS/iPP(DCHT) samples; the Avrami index n for iPP samples at different Tc,iso; the constant parameters of the Lauritzen and Hoffman model; the Tm0 values of α- and β-phases for each iPP (PDF)

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