Effects of Various Mixed Metal ChloridesAlCl3 in TiCl4/MgCl2/THF Catalytic System on Ethylene Polymerization

  • Nittaya Sudsong Center of Excellence on Catalysis and Catalytic Reaction Engineering, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok 10330, Thailand
  • Wanna Phiwkliang Center of Excellence on Catalysis and Catalytic Reaction Engineering, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok 10330, Thailand
  • Bunjerd Jongsomjit Center of Excellence on Catalysis and Catalytic Reaction Engineering, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok 10330, Thailand
  • Piyasan Praserthdam Center of Excellence on Catalysis and Catalytic Reaction Engineering, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok 10330, Thailand
Keywords: Ziegler-Natta catalyst, ethylene polymerization, Lewis acids; TiCl4/MgCl2/THF catalyst

Abstract

In this research, the modification of TiCl4/MgCl2/THF catalyst system with various metal chlorides was investigated on ethylene polymerization. Experimentally, metal chlorides (CaCl2, FeCl2 and ZnCl2) were simultaneously introduced different with TiCl4/MgCl2/THF catalyst. ICP analysis was used to determine the total amount of each metal in the catalyst. For polymerization reaction, TEA was used as cocatalyst and hexane was used as a medium solvent. The Al/Ti molar ratio was 140. The activity result of Ca-Al, Zn-Al and Fe-Al was 979, 1009 and 1476 kgPE/molTi.h, respectively. The coaddition of AlCl3 and FeCl2 in TiCl4/MgCl2/THF catalyst system exhibited the highest activity. It suggested that the co-addition of AlCl3 and FeCl2 has higher electronegativity (EN) and the radius of Fe2+ is closer to Mg2+ resulting in an increased efficiency of the THF removal. This result led to improve the catalyst performance.

References

1. Bialek, M., Ochedzan-Siodlak, W., Dziuber, K., Czaja, K. and Bosowska, K. (2014). Coordination (co)polymerization of olefins, CHEMIK, 68, 268.
2. Chan, Y. and Fan, Z. (2006). Ethylene/1- hexene copolymerization with TiCl4/MgCl2/AlCl3 catalyst in the presence of hydrogen, European Polymer Journal, 42, 2441.
3. Chen, Y., Fan, Z., Liao, J. and Liao, S. (2006). Molecular weight distribution of polyethylene catalyzed by Ziegler– Natta catalyst supported on MgCl2 doped with AlCl3, Journal of Applied Polymer Science, 102, 1768.
4. Chu, K. J., Chang, H. S. and Ihm, S. K. (1994). Effect of diethyl aluminum chloride (DEAC) addition to the catalysts prepared by reduction of TiCl4 with EtMgCl on ethylene- propylene copolymerization, Eur. Polym. J., 30, 1467.
5. Eisch, J. J. (2012). Fifty years of Ziegler– Natta polymerization: from serendipity to science. A personal account, Organometallics, 31, 4917.
6. Grau, E., Lesage, A. Norsic, S. Coperet, C. Monteil, V. and Sautet, P. (2013). Tetrahydrofuran in TiCl4/THF/MgCl2: a non-innocent ligand for supported Ziegler–Natta polymerization catalysts, ACS Catalysis, 3, 52.
7. Jiang, X., Wang, H. Tian, X. Yang, Y. and Fan, Z. (2011). Effects of doping LiCl into MgCl2-supported Ziegler−Natta catalyst on the molecular weight distribution and isotacticity of polypropylene, Ind. Eng. Chem. Res., 50, 259.
8. Kim, J. H. (1995). Copolymerization of ethylene and 1-butene with highly active Ti/Mg bimetallic catalysts. Effect of partial activation by AlEt2Cl, Macromol. Rapid Commun., 16, 113.
9. Luo, H., Tang, R. and Gao, K. (2002). Studies on the formation of new, highly active silica-supported Ziegler– Natta catalyst for ethylene polymerization, Journal of Catalysis, 210, 328.
10. Maria, L. C. (1995). Preparation of Ziegler-Natta catalyst based on TiCi4 modified with metal chlorides for copolymerization of ethylene and propene, Polymer, 36, 2845.
11. Phiwkliang, W., Jongsomjit, B. and Praserthdam, P. (2013). Effect of ZnCl2- and SiCl4-doped TiCl4/MgCl2/THF catalysts for ethylene polymerization, J. APPL. POLYM. SCI., 1588.
12. Phiwkliang, W., Jongsomjit, B. and Praserthdam, P. (2014). Synergistic effects of the ZnCl2-SiCl4 modified TiCl4/MgCl2/THF catalytic system on ethylene/1-hexene and ethylene/1- octene copolymerizations, Chinese Journal of Polymer Science, 32, 84.
13. Pirinen, S., Koshevoy, I. O., Denifl, P. and Pakkanen, T. T. (2013). A single- crystal model for MgCl2-electron donor support materials: [Mg3Cl5(THF)4Bu]2 (Bu = n-Butyl), Organometallics, 32, 4208.
14. Sobota, P. (2004). Metal-assembled compounds: precursors of polymerization catalysts and new materials, Coordination Chemistry Reviews, 248, 1047.
15. Wilke, G. (2003). Fifty years of Ziegler catalysts: consequences and development of an invention, Angew Chem Int Ed Engl, 42, 5000.
Published
2014-12-31
How to Cite
Sudsong, N., Phiwkliang, W., Jongsomjit, B., & Praserthdam, P. (2014). Effects of Various Mixed Metal ChloridesAlCl3 in TiCl4/MgCl2/THF Catalytic System on Ethylene Polymerization. ASEAN Journal of Chemical Engineering, 14(2), 12-18. Retrieved from https://dev.journal.ugm.ac.id/v3/AJChE/article/view/8475
Issue
Vol 14 No 2 (2014)
Section
Articles

Copyright holder for articles is ASEAN Journal of Chemical Engineering. Articles published in ASEAN J. Chem. Eng. are distributed under a Creative Commons Attribution-NonCommercial 4.0 International (CC BY-NC 4.0) license. 

Authors agree to transfer all copyright rights in and to the above work to the ASEAN Journal of Chemical Engineering Editorial Board so that the Editorial Board shall have the right to publish the work for non-profit use in any media or form. In return, authors retain: (1) all proprietary rights other than copyright; (2) re-use of all or part of the above paper in their other work; (3) right to reproduce or authorize others to reproduce the above paper for authors’ personal use or for company use if the source and the journal copyright notice is indicated, and if the reproduction is not made for the purpose of sale.