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Article

Crystallization and Morphology of Triple Crystalline Polyethylene-b-poly(ethylene oxide)-b-poly(ε-caprolactone) PE-b-PEO-b-PCL Triblock Terpolymers

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POLYMAT and Department of Polymers and Advanced Materials: Physics, Chemistry and Technology, University of the Basque Country UPV/EHU, Paseo Manuel Lardizábal 3, 20018 Donostia-San Sebastián, Spain
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Department of Chemical and Environmental Engineering, University of the Basque Country UPV/EHU, Plaza Europa 1, 20018 Donostia-San Sebastián, Spain
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Polymer Synthesis Laboratory, KAUST Catalysis Center, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955, Saudi Arabia
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Department of Chemistry and Industrial Chemistry, University of Genova, via Dodecaneso 31, 16146 Genova, Italy
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Ikerbasque, Basque Foundation for Science, Plaza Euskadi 5, 48009 Bilbao, Spain
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Authors to whom correspondence should be addressed.
Academic Editors: Volker Abetz and Holger Schmalz
Polymers 2021, 13(18), 3133; https://doi.org/10.3390/polym13183133
Received: 2 September 2021 / Revised: 10 September 2021 / Accepted: 13 September 2021 / Published: 16 September 2021
The morphology and crystallization behavior of two triblock terpolymers of polymethylene, equivalent to polyethylene (PE), poly (ethylene oxide) (PEO), and poly (ε-caprolactone) (PCL) are studied: PE227.1-b-PEO4615.1-b-PCL3210.4 (T1) and PE379.5-b-PEO348.8-b-PCL297.6 (T2) (superscripts give number average molecular weights in kg/mol and subscripts composition in wt %). The three blocks are potentially crystallizable, and the triple crystalline nature of the samples is investigated. Polyhomologation (C1 polymerization), ring-opening polymerization, and catalyst-switch strategies were combined to synthesize the triblock terpolymers. In addition, the corresponding PE-b-PEO diblock copolymers and PE homopolymers were also analyzed. The crystallization sequence of the blocks was determined via three independent but complementary techniques: differential scanning calorimetry (DSC), in situ SAXS/WAXS (small angle X-ray scattering/wide angle X-ray scattering), and polarized light optical microscopy (PLOM). The two terpolymers (T1 and T2) are weakly phase segregated in the melt according to SAXS. DSC and WAXS results demonstrate that in both triblock terpolymers the crystallization process starts with the PE block, continues with the PCL block, and ends with the PEO block. Hence triple crystalline materials are obtained. The crystallization of the PCL and the PEO block is coincident (i.e., it overlaps); however, WAXS and PLOM experiments can identify both transitions. In addition, PLOM shows a spherulitic morphology for the PE homopolymer and the T1 precursor diblock copolymer, while the other systems appear as non-spherulitic or microspherulitic at the last stage of the crystallization process. The complicated crystallization of tricrystalline triblock terpolymers can only be fully grasped when DSC, WAXS, and PLOM experiments are combined. This knowledge is fundamental to tailor the properties of these complex but fascinating materials. View Full-Text
Keywords: triblock terpolymers; polyethylene (PE); poly(ethylene oxide) (PEO); poly(ɛ-caprolactone) (PCL); tricrystalline spherulites triblock terpolymers; polyethylene (PE); poly(ethylene oxide) (PEO); poly(ɛ-caprolactone) (PCL); tricrystalline spherulites
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MDPI and ACS Style

Matxinandiarena, E.; Múgica, A.; Zubitur, M.; Ladelta, V.; Zapsas, G.; Cavallo, D.; Hadjichristidis, N.; Müller, A.J. Crystallization and Morphology of Triple Crystalline Polyethylene-b-poly(ethylene oxide)-b-poly(ε-caprolactone) PE-b-PEO-b-PCL Triblock Terpolymers. Polymers 2021, 13, 3133. https://doi.org/10.3390/polym13183133

AMA Style

Matxinandiarena E, Múgica A, Zubitur M, Ladelta V, Zapsas G, Cavallo D, Hadjichristidis N, Müller AJ. Crystallization and Morphology of Triple Crystalline Polyethylene-b-poly(ethylene oxide)-b-poly(ε-caprolactone) PE-b-PEO-b-PCL Triblock Terpolymers. Polymers. 2021; 13(18):3133. https://doi.org/10.3390/polym13183133

Chicago/Turabian Style

Matxinandiarena, Eider, Agurtzane Múgica, Manuela Zubitur, Viko Ladelta, George Zapsas, Dario Cavallo, Nikos Hadjichristidis, and Alejandro J. Müller 2021. "Crystallization and Morphology of Triple Crystalline Polyethylene-b-poly(ethylene oxide)-b-poly(ε-caprolactone) PE-b-PEO-b-PCL Triblock Terpolymers" Polymers 13, no. 18: 3133. https://doi.org/10.3390/polym13183133

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