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Impact of AlCl3 and FeCl2 Addition on Catalytic Behaviors of TiCl4/MgCl2/THF Catalysts for Ethylene Polymerization and Ethylene/1-Hexene Copolymerization

Department of Chemical Engineering, Chulalongkorn University, Bangkok, Thailand

Received: 22 Jan 2018; Revised: 18 Mar 2018; Accepted: 19 Mar 2018; Available online: 14 Nov 2018; Published: 4 Dec 2018.
Editor(s): Hadi Nur
Open Access Copyright (c) 2018 by Authors, Published by BCREC Group under http://creativecommons.org/licenses/by-sa/4.0.

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Abstract

The present research focuses on elucidating of the impact of Lewis acids including AlCl3 and FeCl2 addition on catalytic behaviors during ethylene polymerization and ethylene/1-hexene copolymerization over the TiCl4/MgCl2/THF catalyst (Cat. A). In this study, the Cat. A with the absence and presence of Lewis acids was synthesized via the chemical route. Then, all catalyst samples were characterized and tested in the slurry polymerization. For ethylene polymerization, using the Cat. A with the presence of AlCl3 apparently gave the highest activity among other catalysts. In addition, the activity of catalysts tended to increase with the presence of the Lewis acids. This can be attributed to an enhancement of active center distribution by the addition of Lewis acids leading to larger amounts of the isolated Ti species. Moreover, with the presence of Lewis acids, the effect of hydrogen on the decreased activity was also less pronounced. Considering ethylene/1-hexene copolymerization, it revealed that the catalyst with the presence of mixed Lewis acids (AlCl3 + FeCl2) exhibited the highest activity. It is suggested that the presence of mixed Lewis acids possibly caused a change in acidity of active sites, which is suitable for copolymerization. However, activities of all catalysts in ethylene/1-hexene copolymerization were lower than those in ethylene polymerization. The effect of hydrogen on the decreased activity for both polymerization and copolymerization system was found to be similar with the presence of Lewis acids. Based on this study, it is quite promising to enhance the catalytic activity by addition of proper Lewis acids, especially when the pressure of hydrogen increases. The characteristics of polymers obtained upon the presence of Lewis acids will be discussed further in more detail.  

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Keywords: Ethylene/1-Hexene Copolymerization; Ziegler-Natta Catalysts; Lewis Acid; Linear Low-Density Polyethylene
Funding: Ratchadaphiseksomphot Endowment Fund (2017), Chulalongkorn University for the Postdoctoral Fellowship

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  1. Lee, T., Kim, W.K., Lee, Y., Ryou, M.H., Lee, Y.M. (2014). Effect of Al2O3 Coatings Prepared by RF Sputtering on Polyethylene Separators for High-Power Lithium Ion Batteries. Macromol. Res., 22: 1190-1195
  2. Jeon, M., Han, C.J., Kim, S.Y. (2006). Poly-merizations of Propylene with Unsymmetrical (α-Diimine)nickel(II) Catalysts. Macromol. Res., 14: 306-311
  3. Phiwkliang, W., Jongsomjit, B., Praserthdam, P. (2014). Synergistic Effects of the ZnCl2-SiCl4 Modified TiCl4/MgCl2/THF Catalytic System on Ethylene/1-Hexene and Ethylene/1-Octene Copolymerizations. Chin. J. Polym. Sci., 32: 84-91
  4. Wannaborworn, M., Praserthdam, P., Jongsomjit, B., Cai, Z., Yano, H., Shiono, T. (2013). Copolymerization of Ethylene and 1‐Hexene with Ansa‐Dimethylsilylene (fluorenyl)(t‐butylamido) Dimethyltitanium Complexes Activated by Modified Methyl-aluminoxane. Macromol. Chem. Phys., 214: 2584-2590
  5. Xia, S., Fu, Z., Huang, B., Xu, J., Fan, Z. (2012). Ethylene/1-Hexene Copolymerization with MgCl2-supported Ziegler–Natta Catalysts Containing Aryloxy Ligands. Part I: Catalysts Prepared by Immobilizing TiCl3(OAr) onto MgCl2 in Batch Reaction. J. Mol. Catal. A: Chem., 355: 161-167
  6. Czaja, K., Białek, M., Utrata, A. (2004). Copolymerization of Ethylene with 1‐Hexene over Metallocene Catalyst Supported on Complex of Magnesium Chloride with Tetrahydrofuran. J. Polym. Sci. Part A: Polym. Chem., 42: 2512-2519
  7. Czaja, K., Białek, M. (2001). Microstructure of Ethylene-1-Hexene and Ethylene-1-Octene Copolymers Obtained over Ziegler–Natta Catalysts Supported on MgCl2(THF)2. Polym., 42: 2289-2297
  8. Britto, M.L., Galland, G.B., dos Santos, J.H.Z., Forte, M.C. (2001). Copolymerization of Ethylene and 1-Hexene with Et(Ind)2 ZrCl2 in Hexane. Polym., 42: 6355-6361
  9. Jantasee, S., Shiono, T., Jongsomjit, B. (2013). Copolymerization of Ethylene/1-Hexene with Zirconocene/MAO Catalyst Supported on Spherical Zirconia Modified with BCl3, SiCl4, and Glycerol. Polym. Bull., 70: 1753-1768
  10. Wannaborworn, M., Jongsomjit, B. (2009). Ethylene/1-Octene Copolymerization over Ga-modified SiO2-supported Zirconocene/MMAO Catalyst using in Situ and Ex Situ Impregnation Methods. Iran. Polym. J., 18: 969-979
  11. Chen, Y.P., Fan, Z.Q. (2006). Ethylene/1-Hexene Copolymerization with TiCl4/MgCl2/AlCl3 Catalyst in the Presence of Hydrogen. Eur. Polym. J., 42: 2441-2419
  12. Xia, S.J., Fu, Z.S., Liu, X.Y., Fan, Z.Q. (2013). Copolymerization of Ethylene and 1-Hexene with TiCl4/MgCl2 Catalysts Modified by 2,6-Diisopropylphenol. Chin. J. Polym. Sci., 31: 110-121
  13. Mulhaupt, R., Ovenall, D.W., Ittel, S.D. (1988). Control of Composition in Ethylene Copolymerizations using Magnesium Chloride Supported Ziegler–Natta Catalysts. J. Polym. Sci. Part A: Polym. Chem., 26: 2487-2500
  14. Kong, Y., Yi, J., Dou, X., Liu, W., Huang, Q., Gao, K. (2010). With Different Structure Ligands Heterogeneous Ziegler–Natta Catalysts for the Preparation of Copolymer of Ethylene and 1-Octene with High Comonomer Incorporation. Polym., 51: 3859-3866
  15. Luo, H.K., Tang, R.G., Gao, K.J. (2002). Studies on the Formation of New, Highly Active Silica-Supported Ziegler–Natta Catalyst for Ethylene Polymerization. J. Catal., 210: 328-339
  16. Carlini, C., D'Alessio, A., Giaiacopi, S., Po, R., Pracella, M., Galletti, A.M.R. (2007). Linear Low-Density Polyethylenes by Co-polymerization of Ethylene with 1-Hexene in the Presence of Titanium Precursors and Organoaluminium Co-catalysts. Polym., 48: 1185-1192
  17. Coutinho, F.M.B., Xavier, J.L. (1997). Properties of Ethylene-Propylene Copolymers Synthesized by a Supported Ziegler-Natta Catalyst Based on TiCl4/MgCl2/PCl3. Eur. Polym. J., 33: 897-901
  18. Wang, W., Wang, L., Chen, T., Sun, T.X., Wang, J.J., Chen, X. (2006). Low Isotactic Polypropylene Synthesized with a MgCl2/AlCl3-Supported Ziegler Catalyst. J. Mol. Catal. A: Chem., 244: 146-150
  19. Chu, K.J., Chang, H.S., Ihm, S.K. (1994). Effects of Diethyl Aluminum Chloride (DEAC) Addition to the Catalysts Prepared by Reduction of TiCl4 with EtMgCl on Ethylene-Propylene Copolymerization. Eur. Polym. J., 30:.1467-1472
  20. Kim, J.H., Han, T.K., Choi, H.K., Kim, I., Woo, S.I. (1995). Copolymerization of Ethylene and 1-Butene with Highly Active TI/MG Bimetallic Catalysts. Effect of Partial Activation by AlEt2Cl. Macromol. Rapid Commun., 16: 113-118
  21. Magalhaes, D.T., Do Coutto Filho, O., Coutinho, F. (1991). Ziegler-Natta Catalyst for Ethylene and Propylene Polymerization Supported on Adducts of Magnesium Chloride with Methyl and Ethyl Alcohols. Eur. Polym. J., 27: 827-830
  22. Grau, E., Lesage, A., Norsic, S., Copéret, C., Monteil, V., Sautet, P. (2012). Tetrahydrofuran in TiCl4/THF/MgCl2: a Non-Innocent Ligand for Supported Ziegler–Natta Polymerization Catalysts. ACS Catal., 3: 52-56
  23. Huang, R., Malizia, F., Pennini, G., Koning, C.E., Chadwick, J.C. (2008). Effects of MgCl2 Crystallographic Structure on Active Centre Formation in Immobilized Single‐Centre and Ziegler–Natta Catalysts for Ethylene Polymerization. Macromol. Rapid Commun., 29: 1732-1738
  24. Chang, H.S., Song, W.D., Chu, K.J., Ihm, S.K. (1992). Effects of Removing THF from the TiCl3 (AA)/3MgCl2/THF Catalyst System on the Ethylene-Propylene Copolymerization Mechanism. Macromol., 25: 2086-2092
  25. Phiwkliang, W., Jongsomjit, B., Praserthdam, P. (2013). Effect of ZnCl2‐and SiCl4‐doped TiCl4/MgCl2/THF Catalysts for Ethylene Polymerization. J. Appl. Polym. Sci., 130: 1588-1594
  26. Seenivasan, K., Sommazzi, A., Bonino, F., Bordiga, S., Groppo, E. (2011). Spectroscopic Investigation of Heterogeneous Ziegler–Natta Catalysts: Ti and Mg Chloride Tetrahydrofuranates, Their Interaction Compound, and the Role of the Activator. Chem. Eur. J., 17: 8648-8656
  27. Pothirat, T., Jongsomjit, B., Praserthdam, P. (2008). Effect of Zr-modified SiO2-supported Metallocene/MAO Catalyst on Copolymerization of Ethylene/1-Octene. Catalysis Letters, 121: 266-273
  28. Sudsong, N., Phiwkliang, W., Jongsomjit, B., Praserthdam, P. (2015). Effects of Various Mixed Metal Chlorides-AlCl3 in TiCl4/MgCl2/THF Catalytic System on Ethylene Polymerization. ASEAN Journal of Chemical Engineering, 2: 12-18
  29. Taniike, T., Wada, T., Kouzai, I., Takahashi, S., Terano, M. (2010). Role of Dispersion State of Ti Species in Deactivation of MgCl2-supported Ziegler-Natta Catalysts. Macromol. Res., 18: 839-844
  30. Niyomthai, T., Ratchadaphet, A., Jongsomjit, B., Praserthdam, P. (2018). Influence of Hydrogen on Catalytic Properties of Ziegler‐Natta Catalysts Prepared by Different Methods in Ethylene Polymerization. Adv. Polym. Tech. 37(4): 1030-1035 DOI: 10.1002/adv.21753
  31. Kissin, Y., Mink, R., Nowlin, T. (1999). Ethylene Polymerization Reactions with Ziegler–Natta Catalysts. I. Ethylene Polymerization Kinetics and Kinetic Mechanism. J. Polym. Sci. Part A: Polym. Chem., 37: 4255-4272
  32. Kouzai, I., Liu, B., Wada, T., Terano, M. (2007). Effects of Hydrogen for Different Stereospecific Active Sites on Ultra Low TiCl3 Loading Supported Catalyst. Macromol. React. Eng., 1: 160-164
  33. Kissin, Y.V., Mink, R.I., Nowlin, T.E., Brandolini, A.J. (1999). Kinetics and Mechanism of Ethylene Homopolymerization and Copolymerization Reactions with Heterogeneous Ti-based Ziegler–Natta Catalysts. Top Catal., 7: 69-88
  34. Li, K.T., Dai, C.L., Li, C.Y. (2010). Synthesis of Linear Low Density Polyethylene with a Nano-Sized Silica Supported Cp2ZrCl2/MAO Catalyst. Polym. Bull., 64: 749-759
  35. Brandolini, A.J., Hills, D.D. (2000). NMR Spectra of Polymers and Polymer Additives: CRC Press
  36. Parvez, M.A., Rahaman, M., Suleiman, M., Soares, J., Hussein, I. (2014). Correlation of Polymerization Conditions with Thermal and Mechanical Properties of Polyethylenes Made with Ziegler-Natta Catalysts. Int. J. Polym. Sci. Article ID: 549031, 10 pages
  37. Quijada, R., Scipioni, R.B., Mauler, R.S., Galland, G.B., Miranda, M.S. (1995). Synthesis and Characterization of Ethylene-1-Hexene Copolymers using Homogeneous Ziegler-Natta Catalysts. Polym. Bull., 35: 299-306

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