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Crystallization kinetics of ethylene homopolymers: a new perspective from residual catalyst and resin molecular weight

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Abstract

Two Ziegler-Natta and one metallocene supported catalysts were prepared that were used to synthesize ethylene homopolymers with different molecular weights. The influence of varying residual catalyst types and molecular weights on the isothermal crystallization kinetics of these polymers was studied using DSC and Avrami model to gain better understanding. The MetCat HomoPE, unlike the Z-N HomoPEs, followed the Avrami model during the entire crystallization. The increase in molecular weights did not affect (i) the decreasing trend of 1/t 1/2 (bulk crystallization rate) and K (crystallization rate constant) with the increase in T c (crystallization temperature), and (ii) the increasing trend of K with the increase in %crystallinity. However, combined with the varying residual catalysts, it differently varied the rate of change of 1/t 1/2 and K; and decreased T c . K and 1/t 1/2 turned out to be asymptotically related up to 1/t 1/2  ≈ 0.73 min−1. The residual catalyst type more predominantly affected the crystallization facileness than the molecular weight. Therefore, the Z-N 1 residual catalyst acted as heterogeneous nuclei. In Z-N HomoPE 1 and Z-N HomoPE 2, n ranged from 2.2 to 3.4, and 2.6 to 3.0, respectively as a function of T c . In MetCat HomoPE, it remained constant at 2. Therefore, the MetCat residual catalyst impinged the expected spherulitic crystal growth to a two dimensional one. All these findings were explained considering how the molecular level residual catalysts, with their characteristic surface chemistries and structures, influenced the prevailing heterogeneous nucleation process, and the aliased interaction of G (nuclei growth rate) and Ñ (nucleation rate).

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Acknowledgements

The authors thank the Saudi Arabian Ministry of Higher Education (MOHE) for sponsoring this study through the Center of Research Excellence in Petroleum Refining and Petrochemicals (CoRE-PRP), which was established in April 2007 at King Fahd University of Petroleum & Minerals (KFUPM), Dhahran, Saudi Arabia. The support from the Center of Refining & Petrochemicals (CRP) of KFUPM Research Institute; and the technical assistance of Mr. M. Córdova Universidad Simón Bolívar, Venezuela; Dr. Pilar del Hierro, Polymer Char, Spain are gratefully acknowledged. The useful discussion with Prof. A. J. Müller, Universidad Simón Bolívar, Venezuela is acknowledged, too. The authors also thank PQ Corporation, Philadelphia, USA for donating the silica.

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Authors and Affiliations

  1. Center of Research Excellence in Petroleum Refining & Petrochemicals (CoRE-PRP), King Fahd University of Petroleum & Minerals, Dhahran, 31261, Saudi Arabia

    Muhammad Atiqullah, Ikram Hussain, Abdulrahman Al-Harbi, Atif Fazal & Anwar Hossaen

  2. Center for Refining & Petrochemicals (CRP), King Fahd University of Petroleum & Minerals, Dhahran, 31261, Saudi Arabia

    Muhammad Atiqullah, Ikram Hussain & Anwar Hossaen

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  1. Muhammad Atiqullah
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  2. Ikram Hussain
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  3. Abdulrahman Al-Harbi
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  4. Atif Fazal
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  5. Anwar Hossaen
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Correspondence to Muhammad Atiqullah.

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Atiqullah, M., Hussain, I., Al-Harbi, A. et al. Crystallization kinetics of ethylene homopolymers: a new perspective from residual catalyst and resin molecular weight. J Polym Res 19, 9797 (2012). https://doi.org/10.1007/s10965-011-9797-x

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