Calcium coordination polymer containing dimethylphosphate ligands and exhibiting nucleating properties towards α and Β crystal polymorphs of isotactic polypropylene

Abstract The synthesis, structure and thermal properties of a one-dimensional coordination polymer based on calcium bis(dimethylphosphate) (CaDMP) are reported. The rod-like particles of CaDMP crystallized from water in a monoclinic space group P21/c, and contained Ca[O2P(OCH3)2]2 polymeric chains c...

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Main Authors: Maciej Dębowski, Mateusz Kullas, Krystyna Czaja, Beata Sacher-Majewska, Marcin Bączek, Maciej Dranka, Andrzej Ostrowski, Zbigniew Florjańczyk
Format: Article
Language:English
Published: Nature Portfolio 2025-05-01
Series:Scientific Reports
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Online Access:https://doi.org/10.1038/s41598-025-99757-4
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author Maciej Dębowski
Mateusz Kullas
Krystyna Czaja
Beata Sacher-Majewska
Marcin Bączek
Maciej Dranka
Andrzej Ostrowski
Zbigniew Florjańczyk
author_facet Maciej Dębowski
Mateusz Kullas
Krystyna Czaja
Beata Sacher-Majewska
Marcin Bączek
Maciej Dranka
Andrzej Ostrowski
Zbigniew Florjańczyk
author_sort Maciej Dębowski
collection DOAJ
description Abstract The synthesis, structure and thermal properties of a one-dimensional coordination polymer based on calcium bis(dimethylphosphate) (CaDMP) are reported. The rod-like particles of CaDMP crystallized from water in a monoclinic space group P21/c, and contained Ca[O2P(OCH3)2]2 polymeric chains consisting of the octahedrally coordinated Ca2+ ions bridged by the tridentate dimethylphosphate ligands. The variable temperature powder X-ray diffraction measurements showed that this structure undergoes anisotropic thermal expansion upon heating, with no polymorphic transitions occurring up to 190 °C. Thermolysis of CaDMP began around 260 °C leading to the formation of calcium condensed phosphates and volatile oxophosphorus species. A detailed differential scanning calorimetry (DSC) analysis, combined with a fitting of the experimental data to the Avrami or Liu–Mo kinetic models, revealed that CaDMP accelerates isothermal and non-isothermal crystallization of isotactic polypropylene (iPP). DSC and wide-angle X-ray scattering measurements confirmed the presence of α-iPP and β-iPP crystal domains in the systems loaded with CaDMP particles. The crystallographic analysis indicated that β-iPP polymorph formed via epitaxial crystallization on the surface of CaDMP crystals. Mechanical tests proved that the CaDMP-containing composites exhibited better ductility and impact strength than neat iPP.
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spelling doaj-art-50f693d0513e4d2291f04a91cfa2a19a2025-08-20T01:47:32ZengNature PortfolioScientific Reports2045-23222025-05-0115111910.1038/s41598-025-99757-4Calcium coordination polymer containing dimethylphosphate ligands and exhibiting nucleating properties towards α and Β crystal polymorphs of isotactic polypropyleneMaciej Dębowski0Mateusz Kullas1Krystyna Czaja2Beata Sacher-Majewska3Marcin Bączek4Maciej Dranka5Andrzej Ostrowski6Zbigniew Florjańczyk7Faculty of Chemistry, Warsaw University of TechnologyInstitute of Chemistry, University of OpoleInstitute of Chemistry, University of OpoleInstitute of Chemistry, University of OpoleFaculty of Materials, Civil and Environmental Engineering, University of Bielsko-BiałaFaculty of Chemistry, Warsaw University of TechnologyFaculty of Chemistry, Warsaw University of TechnologyFaculty of Chemistry, Warsaw University of TechnologyAbstract The synthesis, structure and thermal properties of a one-dimensional coordination polymer based on calcium bis(dimethylphosphate) (CaDMP) are reported. The rod-like particles of CaDMP crystallized from water in a monoclinic space group P21/c, and contained Ca[O2P(OCH3)2]2 polymeric chains consisting of the octahedrally coordinated Ca2+ ions bridged by the tridentate dimethylphosphate ligands. The variable temperature powder X-ray diffraction measurements showed that this structure undergoes anisotropic thermal expansion upon heating, with no polymorphic transitions occurring up to 190 °C. Thermolysis of CaDMP began around 260 °C leading to the formation of calcium condensed phosphates and volatile oxophosphorus species. A detailed differential scanning calorimetry (DSC) analysis, combined with a fitting of the experimental data to the Avrami or Liu–Mo kinetic models, revealed that CaDMP accelerates isothermal and non-isothermal crystallization of isotactic polypropylene (iPP). DSC and wide-angle X-ray scattering measurements confirmed the presence of α-iPP and β-iPP crystal domains in the systems loaded with CaDMP particles. The crystallographic analysis indicated that β-iPP polymorph formed via epitaxial crystallization on the surface of CaDMP crystals. Mechanical tests proved that the CaDMP-containing composites exhibited better ductility and impact strength than neat iPP.https://doi.org/10.1038/s41598-025-99757-4Hybrid polymerCalcium diorganophosphateIsotactic polypropyleneCrystallizationNucleating agentPolymer composite
spellingShingle Maciej Dębowski
Mateusz Kullas
Krystyna Czaja
Beata Sacher-Majewska
Marcin Bączek
Maciej Dranka
Andrzej Ostrowski
Zbigniew Florjańczyk
Calcium coordination polymer containing dimethylphosphate ligands and exhibiting nucleating properties towards α and Β crystal polymorphs of isotactic polypropylene
Scientific Reports
Hybrid polymer
Calcium diorganophosphate
Isotactic polypropylene
Crystallization
Nucleating agent
Polymer composite
title Calcium coordination polymer containing dimethylphosphate ligands and exhibiting nucleating properties towards α and Β crystal polymorphs of isotactic polypropylene
title_full Calcium coordination polymer containing dimethylphosphate ligands and exhibiting nucleating properties towards α and Β crystal polymorphs of isotactic polypropylene
title_fullStr Calcium coordination polymer containing dimethylphosphate ligands and exhibiting nucleating properties towards α and Β crystal polymorphs of isotactic polypropylene
title_full_unstemmed Calcium coordination polymer containing dimethylphosphate ligands and exhibiting nucleating properties towards α and Β crystal polymorphs of isotactic polypropylene
title_short Calcium coordination polymer containing dimethylphosphate ligands and exhibiting nucleating properties towards α and Β crystal polymorphs of isotactic polypropylene
title_sort calcium coordination polymer containing dimethylphosphate ligands and exhibiting nucleating properties towards α and β crystal polymorphs of isotactic polypropylene
topic Hybrid polymer
Calcium diorganophosphate
Isotactic polypropylene
Crystallization
Nucleating agent
Polymer composite
url https://doi.org/10.1038/s41598-025-99757-4
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