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Promoting ethylene polymerization through cocatalyst modification

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Abstract

Effect of chlorocyclohexane (CHC) on ethylene polymerization using MgCl2/TiCl4/TEA Ziegler–Natta catalyst system was studied, where MgCl2, TiCl4, and TEA (triethyl aluminum) were used as support, catalyst, and activator, respectively. The polymerization rate, catalyst activity, and produced polymer were significantly affected by the presence of CHC as a promoter. This study strongly indicates that CHC will act as a promoter with high performance in the ethylene polymerization. There was a remarkable increase in the catalyst yield and polymerization rate, particularly, in the presence of hydrogen which was used for controlling the molecular weight. A reduction in the polymer molecular weight was observed in the presence of CHC and hydrogen. The amount of the produced wax as a byproduct noticeably reduced. The morphology of the polymers was evaluated through scanning electron microscopy and particle size distribution.

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References

  1. Abedi S, Haddadi-Asl V (2007) Olefin coordination polymerization, 1st edn. NPC press, Tehran

    Google Scholar 

  2. Moore EP (1996) Polypropylene handbook, 1st edn. Hanser, Munich

    Google Scholar 

  3. Johnson LK, Mecking S, Brookhart M (1996) Copolymerization of ethylene and propylene with functionalized vinyl monomers by palladium (II) catalysts. J Am Chem Soc 118:267

    Article  CAS  Google Scholar 

  4. Johnson LK, Killian CM, Brookhart M (1995) New Pd(II)- and Ni(II)-based catalysts for polymerization of ethylene and alpha-olefins. J Am Chem Soc 117:6414

    Article  CAS  Google Scholar 

  5. Bohm L (1997) Process for the preparation of a poly-1-olefin. U.S. Pat. 5648309

  6. Bohm L, Berthold J (2004) Method for producing a poly-1-olefin in the presence of a Ziegler catalyst. US Pat 2005/0239978A1

  7. Frank P, Bohm L, Friedhelm G (2004) Modified Ziegler catalyst, process for preparing it and process for preparing poly-1-olefins in its presence. WO 2004/018529 A2

  8. Mousavi M, Hakim S, Nekoomanesh M (2006) Effect of fatty amine and perfluorocarbon as anti-fouling agent on the catalyst activity and titanium oxidation state in slurry polymerization of ethylene. J Appl Polym Sci 102:257

    Article  CAS  Google Scholar 

  9. Lu HK, Tang RG, Yang H, Zhao QF, An JY (2000) Studies on highly efficient promoters for titanium-based Ziegler–Natta catalyst for ethylene polymerization. Appl Catal A Gen 203:269

    Article  Google Scholar 

  10. Miserque O, Siraux D, Bodart P (2008) Olefin polymerization process in the presence of an anti-fouling agent. US Pat 2008/0119622

  11. Siraux D, Dewachter D (2011) Process for preparing polyolefins and use of antifouling agents therein. E.P. 2011/063147

  12. Hogan JP (1991) Process for preventing fouling in a gas phase polymerization reactor. US Pat 5026795 A

  13. Reinking MK, Bauer PD, Seyler JW (1999) A study of halocarbon promoter influence on catalyst reactivity and polymer Mn in vanadium-based ethylene polymerizations. Appl Catal A Gen 189:23

    Article  CAS  Google Scholar 

  14. Bahri-Laleh N, Arabi H, Mehdipor-Ataei S, Nekoomanesh-Haghighi M, Zohuri G, Seifali M, Akbari Z (2012) Activation of Ziegler–Natta catalysts by organohalide promoters: a combined experimental and density functional theory study. J Appl Polym Sci 123:2526

    Article  CAS  Google Scholar 

  15. Abedi S, Azadi F, Dafteri-Besheli M, Majdabadi-Farahani N, Safinejad A (2014) A butyl chloride as promoter in ethylene polymerization by magnesium ethoxide-supported catalyst. J Appl Polym Sci. doi:10.1002/app.40189

    Google Scholar 

  16. Zoeckler MT, Karol FJ (1989) Ethylene polymerization catalyst. US Pat 4812432

  17. Yang Y, Kim H, Lee J, Paik H, Jang HG (2000) Roles of chloro compound in homogeneous [Cr(2-ethylhexanoate)3/2,5-dimethylpyrrole/triethylaluminum/chloro compound] catalyst system for ethylene trimerization. Appl Catal A Gen 193:29

    Article  CAS  Google Scholar 

  18. Abedi S, Hassanpour N (2006) Preparation of bimodal polypropylene in two-step polymerization. J Appl Polym Sci 101:1456

    Article  CAS  Google Scholar 

  19. Farrer DK, Moore GE, Noble LA (2003) Process for the polymerization of ethylene and inter polymers therefor. US Pat 6635726 B2

  20. Chamla C, Daire E (1992) Supported polyolefin catalyst for the (co)polymerization of ethylene in gas phase. US Pat 5166281

  21. Kang KK, Shiono T, Jeong Y, Lee D (1999) Polymerization of propylene by using Mg(OEt)2–DNBP–TiCl4 catalyst with alkoxy disilanes as external donor. J Appl Polym Sci 71:293

    Article  CAS  Google Scholar 

  22. Vogel AI (1978) Textbook of quantitative inorganic analysis, 4th edn. London, Longman

    Google Scholar 

  23. Kashiwa N, Yoshitake Y (1984) The influence of the valence state of titanium in MgCl2-supported titanium catalysts on olefin polymerization. Macromol Chem 185:1133

    Article  CAS  Google Scholar 

  24. Inoue M (1963) Studies on crystallization of high polymers by differential thermal analysis. J Polym Sci Part A Gen Papers 1:2697

    Article  CAS  Google Scholar 

  25. Abedi S, Abdouss M, Nekoomanesh-Haghighi M, Sarifir-Sanjani N (2013) PE/clay nanocomposites produced via in situ polymerization by highly active clay-supported Ziegler–Natta catalyst. Polym Bull 70:1313

    Article  CAS  Google Scholar 

  26. Salajka Z, Kratochvila J, Hude P, Vecorek P (1993) One-phase supported titanium-based catalysts for polymerization of ethylene. II. Effect of hydrogen. J Polym Sci Part A Polym Chem 31:1493

    Article  CAS  Google Scholar 

  27. Bahri-Laleh N, Seifali M, Nekoomanesh-Haghighi M, Akbari Z, Tavasoli MR, Mirjahanmardi SH (2010) Effect of halocarbon promoters on polyethylene properties using MgCl2 (ethoxide type)/TiCl4/AlEt3/H2 catalyst system. J Appl Polym Sci 117:1780

    CAS  Google Scholar 

  28. Chien JC, Nozaki T (1991) High activity magnesium chloride supported catalysts for olefin polymerization. XXIX. Molecular basis of hydrogen activation of magnesium chloride supported Ziegler–Natta catalysts. J Polym Sci Part A Polym Chem 29:505

    Article  CAS  Google Scholar 

  29. Nikolaeva MI, Mikenas TB, Matsko MA, Echevskaya LG, Zakharov VA (2011) Ethylene polymerization over supported titanium–magnesium catalysts: effect of polymerization parameters on the molecular weight distribution of polyethylene. J Appl Polym Sci 122:3092

    Article  CAS  Google Scholar 

  30. Chu KJ, Soares JBP, Penlidis A, Ihm SK (2000) Effect of prepolymerization and hydrogen pressure on the microstructure of ethylene/1-hexene copolymers made with MgCl2-supported TiCl3 catalysts. Eur Polym J 36:3

    Article  CAS  Google Scholar 

  31. Abedi S, Abdouss M, Nekoomanesh-Haghighi M, Sarifir-Sanjani N (2013) New clay-supported Ziegler–Natta catalyst for preparation of PE/Clay nanocomposites via in situ polymerization. J Appl Polym Sci 128:1879

    CAS  Google Scholar 

  32. Monji M, Abedi S, Pormahdian S, Afshar-Taromi F (2009) Effect of prepolymerization on propylene polymerization. J Appl Polym Sci 112:1863

    Article  CAS  Google Scholar 

  33. Cecchin G, Marchetti E, Baruzzi G (2001) On the mechanism of polypropene growth over MgCl2/TiCl4 catalyst systems. Macromol Chem Phys 202:1987

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors wish to express their gratitude to the Petrochemical Research and Technology Co. of NPC for its financial support. We would also like to thank Z. Hasanvand, S.R. Nokhbeh, S. Mohammadi, N. Zare, L. Baharmand, M. R. Seddigh-e-rad and S. M. Beheshti for their help.

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Authors and Affiliations

  1. National Petrochemical Company, Petrochemical Research and Technology Company, P.O. Box 1435884711, Tehran, Iran

    Sadegh Abedi, Noushin Majdabadi-Farahani, Majid Daftari-Besheli & Farhad Azadi

  2. Department of Biotechnology-Chemical Engineering, Science and Research Branch, Islamic Azad University, Bākhtarān, Iran

    Noushin Majdabadi-Farahani, Majid Daftari-Besheli & Hamidreza Ghasempour

Authors
  1. Sadegh Abedi
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  2. Noushin Majdabadi-Farahani
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  3. Majid Daftari-Besheli
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  4. Hamidreza Ghasempour
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  5. Farhad Azadi
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Correspondence to Sadegh Abedi.

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Abedi, S., Majdabadi-Farahani, N., Daftari-Besheli, M. et al. Promoting ethylene polymerization through cocatalyst modification. Polym. Bull. 72, 2377–2388 (2015). https://doi.org/10.1007/s00289-015-1410-8

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  • DOI: https://doi.org/10.1007/s00289-015-1410-8

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