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

Handle URI:
http://hdl.handle.net/10754/593139
Title:
Sequential crystallization and morphology of triple crystalline biodegradable PEO-b-PCL-b-PLLA triblock terpolymers
Authors:
Palacios, Jordana; Mugica, Agurtzane; Zubitur, Manuela; Iturrospe, Amaia; Arbe, A.; Liu, Guoming; Wang, Dujin; Zhao, Junpeng; Hadjichristidis, Nikolaos ( 0000-0003-1442-1714 ) ; Muller, Alejandro
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.
KAUST Department:
Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)
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 Adv.
Issue Date:
5-Jan-2016
DOI:
10.1039/C5RA25812J
Type:
Article
ISSN:
2046-2069
Additional Links:
http://pubs.rsc.org/en/Content/ArticleLanding/2016/RA/C5RA25812J
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorPalacios, Jordanaen
dc.contributor.authorMugica, Agurtzaneen
dc.contributor.authorZubitur, Manuelaen
dc.contributor.authorIturrospe, Amaiaen
dc.contributor.authorArbe, A.en
dc.contributor.authorLiu, Guomingen
dc.contributor.authorWang, Dujinen
dc.contributor.authorZhao, Junpengen
dc.contributor.authorHadjichristidis, Nikolaosen
dc.contributor.authorMuller, Alejandroen
dc.date.accessioned2016-01-10T10:08:22Zen
dc.date.available2016-01-10T10:08:22Zen
dc.date.issued2016-01-05en
dc.identifier.citationSequential crystallization and morphology of triple crystalline biodegradable PEO-b-PCL-b-PLLA triblock terpolymers 2016 RSC Adv.en
dc.identifier.issn2046-2069en
dc.identifier.doi10.1039/C5RA25812Jen
dc.identifier.urihttp://hdl.handle.net/10754/593139en
dc.description.abstractThe 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.en
dc.language.isoenen
dc.publisherRoyal Society of Chemistry (RSC)en
dc.relation.urlhttp://pubs.rsc.org/en/Content/ArticleLanding/2016/RA/C5RA25812Jen
dc.rightsArchived with thanks to RSC Adv.en
dc.titleSequential crystallization and morphology of triple crystalline biodegradable PEO-b-PCL-b-PLLA triblock terpolymersen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalRSC Adv.en
dc.eprint.versionPost-printen
dc.contributor.institutionPOLYMAT and Polymer Science and Technology Department, Faculty of Chemistry, University of the Basque Country UPV/EHU, Paseo Manuel de Lardizabal 3, 20018 Donostia-San Sebastián, Spainen
dc.contributor.institutionChemical and Environmental Engineering Department, Polytechnic School, University of the Basque Country UPV/EHU, 20018 Donostia-San Sebastián, Spainen
dc.contributor.institutionMaterials Physics Center (CSIC-UPV/EHU), Paseo Manuel de Lardizabal 5, 20018 Donostia-San Sebastián, Spainen
dc.contributor.institutionBeijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, Chinaen
dc.contributor.institutionIKERBASQUE, Basque Foundation for Science, Bilbao, Spainen
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorZhao, Junpengen
kaust.authorHadjichristidis, Nikolaosen
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