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Dimethylformamide Impurities as Propylene Polymerization Inhibitor.

Joaquín Hernández-Fernández1,2,3, Rafael González-Cuello4, Rodrigo Ortega-Toro4

  • 1Chemistry Program, Department of Natural and Exact Sciences, San Pablo Campus, University of Cartagena, Cartagena 130015, Colombia.

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|September 28, 2023
PubMed
Summary

Dimethylformamide (DMF) inhibits Ziegler-Natta catalyzed propylene polymerization by strongly binding to titanium centers. Increasing DMF concentration reduces catalyst activity and alters polymer properties like melt flow index.

Keywords:
N,N-dimethylformamide (DMF)Ziegler–Natta catalystcatalyst inhibitiondensity functional theory (DFT)melt flow index (MFI)molecular weight distribution (MW)polypropyleneproductivity

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Area of Science:

  • Polymer Chemistry
  • Catalysis Science
  • Materials Science

Background:

  • Ziegler-Natta catalysts are crucial for olefin polymerization.
  • Understanding inhibitor effects is key to controlling polymer properties.
  • Dimethylformamide (DMF) is investigated as a potential polymerization inhibitor.

Purpose of the Study:

  • To investigate the impact of dimethylformamide (DMF) on propylene polymerization using Ziegler-Natta catalysts.
  • To analyze how DMF affects catalyst activity, polymer molecular weight, and branching.
  • To determine the interaction mechanism between DMF and the catalyst system.

Main Methods:

  • Experimental polymerization runs with varying DMF concentrations.
  • Analysis of catalyst activity, polymer molecular weight, and melt flow index (MFI).
  • Computational methods including adsorption energy and molecular orbital calculations.

Main Results:

  • Catalyst activity significantly decreases with increasing DMF/Ti ratio.
  • Melt flow index (MFI) loss of 75% observed at 89.92 ppm DMF, indicating increased flowability.
  • DMF shows a strong affinity for the titanium center (adsorption energy ~ -46.157 kcal/mol) compared to propylene (~ -5.2 kcal/mol).

Conclusions:

  • Dimethylformamide (DMF) acts as an effective inhibitor in Ziegler-Natta catalyzed propylene polymerization.
  • The strong binding affinity of DMF to the catalyst's titanium center is the primary mechanism of inhibition.
  • The interaction is further supported by favorable HOMO-SOMO energy gaps, influencing polymerization kinetics and polymer characteristics.