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    Sequential crystallization and morphology of triple crystalline biodegradable PEO-b-PCL-b-PLLA triblock terpolymers

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    Type
    Article
    Authors
    Palacios, Jordana
    Mugica, Agurtzane
    Zubitur, Manuela
    Iturrospe, Amaia
    Arbe, A.
    Liu, Guoming cc
    Wang, Dujin
    Zhao, Junpeng cc
    Hadjichristidis, Nikos cc
    Muller, Alejandro
    KAUST Department
    Biological and Environmental Sciences and Engineering (BESE) Division
    Chemical Science Program
    KAUST Catalysis Center (KCC)
    Physical Science and Engineering (PSE) Division
    Polymer Synthesis Laboratory
    Date
    2016
    Permanent link to this record
    http://hdl.handle.net/10754/593139
    
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    Abstract
    The sequential crystallization of poly(ethylene oxide)-b-poly(e-caprolactone)-b-poly(L-lactide) (PEO-b-PCL-b-PLLA) triblock terpolymers, in which the three blocks are able to crystallize separately and sequentially from the melt, is presented. Two terpolymers with identical PEO and PCL block lengths and two different PLLA block lengths were prepared, thus the effect of increasing PLLA content on the crystallization behavior and morphology was evaluated. Wide angle X-Ray scattering (WAXS) experiments performed on cooling from the melt confirmed the triple crystalline nature of these terpolymers and revealed that they crystallize in sequence: the PLLA block crystallizes first, then the PCL block, and finally the PEO block. Differential scanning calorimetry (DSC) analysis further demonstrated that the three blocks can crystallize from the melt when a low cooling rate is employed. The crystallization process takes place from a homogenous melt as indicated by small angle X-Ray scattering (SAXS) experiments. The crystallization and melting enthalpies and temperatures of both PEO and PCL blocks decrease as PLLA content in the terpolymer increases. Polarized light optical microscopy (PLOM) demonstrated that the PLLA block templates the morphology of the terpolymer, as it forms spherulites upon cooling from the melt. The subsequent crystallization of PCL and PEO blocks occurs inside the interlamellar regions of the previously formed PLLA block spherulites. In this way, unique triple crystalline mixed spherulitic superstructures have been observed for the first time. As the PLLA content in the terpolymer is reduced the superstructural morphology changes from spherulites to a more axialitic-like structure.
    Citation
    Sequential crystallization and morphology of triple crystalline biodegradable PEO-b-PCL-b-PLLA triblock terpolymers 2016 RSC Adv.
    Publisher
    Royal Society of Chemistry (RSC)
    Journal
    RSC Advances
    DOI
    10.1039/C5RA25812J
    Additional Links
    http://pubs.rsc.org/en/Content/ArticleLanding/2016/RA/C5RA25812J
    ae974a485f413a2113503eed53cd6c53
    10.1039/C5RA25812J
    Scopus Count
    Collections
    Articles; Biological and Environmental Science and Engineering (BESE) Division; Physical Science and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

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