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    Sequential Crystallization and Multicrystalline Morphology in PE-b-PEO-b-PCL-b-PLLA Tetrablock Quarterpolymers

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    Type
    Article
    Authors
    Matxinandiarena, Eider
    Múgica, Agurtzane
    Tercjak, Agnieszka cc
    Ladelta, Viko cc
    Zapsas, Georgios cc
    Hadjichristidis, Nikos cc
    Cavallo, Dario cc
    Flores, Araceli cc
    Müller, Alejandro J. cc
    KAUST Department
    Chemical Science Program
    KAUST Catalysis Center (KCC)
    Physical Science and Engineering (PSE) Division
    Polymer Synthesis Laboratory
    Date
    2021-07-23
    Online Publication Date
    2021-07-23
    Print Publication Date
    2021-08-10
    Embargo End Date
    2022-07-23
    Submitted Date
    2021-06-01
    Permanent link to this record
    http://hdl.handle.net/10754/670566
    
    Metadata
    Show full item record
    Abstract
    We investigate for the first time the morphology and crystallization of two novel tetrablock quarterpolymers of polyethylene (PE), poly(ethylene oxide) (PEO), poly(ε-caprolactone) (PCL), and poly(l-lactide) (PLLA) with four potentially crystallizable blocks: PE187.1-b-PEO3715.1-b-PCL2610.4-b-PLLA197.6 (Q1) and PE299.5-b-PEO268.8-b-PCL237.6-b-PLLA227.3 (Q2) (superscripts give number average molecular weights in kg/mol, and subscripts give the composition in wt %). Their synthesis was performed by a combination of polyhomologation (C1 polymerization) and ring-opening polymerization techniques using a ″catalyst-switch″ strategy, either ″organocatalyst/metal catalyst switch″ (Q1 sample, 96% isotactic tetrads) or ″organocatalyst/organocatalyst switch″ (Q2 sample, 84% isotactic tetrads). Their corresponding precursors—triblock terpolymers PE-b-PEO-b-PCL, diblock copolymers PE-b-PEO, and PE homopolymers—were also studied. Cooling and heating rates from the melt at 20 °C/min were employed for most experiments: differential scanning calorimetry (DSC), polarized light optical microscopy (PLOM), in situ small-angle X-ray scattering/wide-angle X-ray scattering (SAXS/WAXS), and atomic force microscopy (AFM). The direct comparison of the results obtained with these different techniques allows the precise identification of the crystallization sequence of the blocks upon cooling from the melt. SAXS indicated that Q1 is melt miscible, while Q2 is weakly segregated in the melt but breaks out during crystallization. According to WAXS and DSC results, the blocks follow a sequence as they crystallize: PLLA first, then PE, then PCL, and finally PEO in the case of the Q1 quarterpolymer; in Q2, the PLLA block is not able to crystallize due to its low isotacticity. Although the temperatures at which the PEO and PCL blocks and the PE and PLLA blocks crystallize overlap, the analysis of the intensity changes measured by WAXS and PLOM experiments allows identifying each of the crystallization processes. The quarterpolymer Q1 remarkably self-assembles during crystallization into tetracrystalline banded spherulites, where four types of different lamellae coexist. Nanostructural features arising upon sequential crystallization are found to have a relevant impact on the mechanical properties. Nanoindentation measurements show that storage modulus and hardness of the Q1 quarterpolymer significantly deviate from those of the stiff PE and PLLA blocks, approaching typical values of compliant PEO and PCL. Results are mainly attributed to the low crystallinity of the PE and PLLA blocks. Moreover, the Q2 copolymer exhibits inferior mechanical properties than Q1, and this can be related to the PE block within Q1 that has thinner crystal lamellae according to its much lower melting point.
    Citation
    Matxinandiarena, E., Múgica, A., Tercjak, A., Ladelta, V., Zapsas, G., Hadjichristidis, N., … Müller, A. J. (2021). Sequential Crystallization and Multicrystalline Morphology in PE-b-PEO-b-PCL-b-PLLA Tetrablock Quarterpolymers. Macromolecules. doi:10.1021/acs.macromol.1c01186
    Sponsors
    This work has received funding from MINECO through projects MAT2017-83014-C2-1-P and MAT2017-88382-P, from the Basque Government through grant IT1309-19, and from the ALBA synchrotron facility through granted proposal u2020084441 (March 2020). We would like to thank the financial support provided by the BIODEST project; this project has received funding from the European Union’s Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreement no. 778092
    Publisher
    American Chemical Society (ACS)
    Journal
    Macromolecules
    DOI
    10.1021/acs.macromol.1c01186
    Additional Links
    https://pubs.acs.org/doi/10.1021/acs.macromol.1c01186
    ae974a485f413a2113503eed53cd6c53
    10.1021/acs.macromol.1c01186
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

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