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<p>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 <i>P</i>2<sub>1</sub>/<i>c</i>, and contained Ca[O<sub>2</sub>P(OCH<sub>3</sub>)<sub>2</sub>]<sub>2</sub> polymeric chains consisting of the octahedrally coordinated Ca<sup>2+</sup> 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&#xa0;°C. Thermolysis of CaDMP began around 260&#xa0;°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.</p>

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

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年5月2日

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  • Maciej Dębowski,
  • Mateusz Kullas,
  • Krystyna Czaja,
  • Beata Sacher-Majewska,
  • Marcin Bączek,
  • Maciej Dranka,
  • Andrzej Ostrowski,
  • Zbigniew Florjańczyk

摘要

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.