Surface science studies of Ziegler-Natta olefin polymerization system: Correlations between polymerization kinetics, polymer structures, and active site structures on model catalysts

Kim, Seong Han; Tewell, Craig R.; Somorjai, Gabor A.

doi:10.1007/BF02706867

Surface science studies of Ziegler-Natta olefin polymerization system: Correlations between polymerization kinetics, polymer structures, and active site structures on model catalysts

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Published: January 2002

Volume 19, pages 1–10, (2002)
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Korean Journal of Chemical Engineering Aims and scope Submit manuscript

Seong Han Kim¹^nAff2,
Craig R. Tewell¹ &
Gabor A. Somorjai¹

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Abstract

The surface composition and structure of model Ziegler-Natta catalysts, polymerizing α-olefins to produce polyolefins, have been studied using modern surface science techniques and compared with their polymerization behaviors. Two types of thin films — TiCl_x/MgCl₂ and TiCl_y/Au — were fabricated on an inert gold substrate, using chemical vapor deposition methods, to model the high-yield catalysts of MgCl₂-supported TiCl₄ and TiCl₃-based catalysts, respectively. The model catalysts could be activated by exposure to triethylaluminum (AlFt₃) vapor. Once activated, both catalysts were active for polymerization of ethylene and propylene in the absence of excess AlEt₃ during polymerization. The model catalysts had polymerization activities comparable to the high-surface-area industrial catalysts. Though both catalysts were terminated with chlorine at the surface, each catalyst assumed different surface structures. The TiCl_x/MgCl₂ film surface was composed of two structures: the (001) basal plane of these halide crystallites and a non-basal plane structure. The TiCl_y/Au film surface assumed only the non-basal plane structure. These structural differences resulted in different tacticity of the polypropylene produced with these catalysts. The TiCl_x/MgCl₂ catalyst produced both atactic and isotactic polypropylene, while the TiCl_y/Au catalyst without the MgCl₂ support produced exclusively isotactic polypropylene. The titanium oxidation state distribution did not have a critical role in determining the tacticity of the polypropylene.

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Polymerization Kinetics of Propylene with the MgCl2-Supported Ziegler-Natta Catalysts—Active Centers with Different Tacticity and Fragmentation of the Catalyst

Article 24 August 2020

The effect of SiO2 calcination temperature and [Si]/[Mg] molar ratio on the performance of bi-supported Ziegler-Natta catalysts in ethylene polymerizations

Article 18 January 2023

Intermetallic PdZn nanoparticles catalyze the continuous-flow hydrogenation of alkynols to cis-enols

Article Open access 13 December 2021

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Seong Han Kim (Assistant Professor)
Present address: Department of Chemical Engineering, The Pennsylvania State University, 16803, University Park, PA, USA

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Department of Chemistry, University of California at Berkeley and Materials Science Division, Lawrence Berkeley National Laboratory, 94720, Berkeley, CA, USA
Seong Han Kim (Assistant Professor), Craig R. Tewell & Gabor A. Somorjai

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Seong Han Kim
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Correspondence to Gabor A. Somorjai.

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Kim, S.H., Tewell, C.R. & Somorjai, G.A. Surface science studies of Ziegler-Natta olefin polymerization system: Correlations between polymerization kinetics, polymer structures, and active site structures on model catalysts. Korean J. Chem. Eng. 19, 1–10 (2002). https://doi.org/10.1007/BF02706867

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Issue Date: January 2002
DOI: https://doi.org/10.1007/BF02706867

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Surface science studies of Ziegler-Natta olefin polymerization system: Correlations between polymerization kinetics, polymer structures, and active site structures on model catalysts

Abstract

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Polymerization Kinetics of Propylene with the MgCl2-Supported Ziegler-Natta Catalysts—Active Centers with Different Tacticity and Fragmentation of the Catalyst

The effect of SiO2 calcination temperature and [Si]/[Mg] molar ratio on the performance of bi-supported Ziegler-Natta catalysts in ethylene polymerizations

Intermetallic PdZn nanoparticles catalyze the continuous-flow hydrogenation of alkynols to cis-enols

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Surface science studies of Ziegler-Natta olefin polymerization system: Correlations between polymerization kinetics, polymer structures, and active site structures on model catalysts

Abstract

Access this article

Similar content being viewed by others

Polymerization Kinetics of Propylene with the MgCl2-Supported Ziegler-Natta Catalysts—Active Centers with Different Tacticity and Fragmentation of the Catalyst

The effect of SiO2 calcination temperature and [Si]/[Mg] molar ratio on the performance of bi-supported Ziegler-Natta catalysts in ethylene polymerizations

Intermetallic PdZn nanoparticles catalyze the continuous-flow hydrogenation of alkynols to cis-enols

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