Effects of FeCl3 doping on the performance of MgCl2/TiCl4/DNPB catalyst in 1-hexene polymerization

Document Type: Original research

Authors

1 Polymerization Engineering Department, Iran Polymer and Petrochemical Institute (IPPI), P.O. Box 14965/115, Tehran, Iran

2 Department of Chemical Engineering, Central Tehran Branch, Islamic Azad University, Tehran, Iran

Abstract

The aim of this study was to examine the effect of catalyst doping on the performance of MgCl2. EtOH/TiCl4 catalyst system. In this regard, a series of undoped as well as FeCl3-doped catalysts was prepared and employed in 1-hexene polymerization. A modified catalyst containing 10 wt. % of FeCl3 dopant demonstrated the highest activity, with 32% activity increase compared to unmodified one, among the series. The GPC results showed a lower molecular weight as well as broader MWD for the poly1-hexenes obtained from FeCl3-doped catalyst. The distribution of active centers was analyzed using deconvolution of the MW profiles with using multiple Flory functions. It was demonstrated that the number of active sites increased by 10 wt. % FeCl3 doping, however, by more increasing the dopant amount to 15 wt.%, the number of active sites decreased. The 13C-NMR results indicated that, FeCl3 doping did not have a considerable effect on the polymer tacticity (with total tacticity of 53 %), however it increased by donor presence to the maximum value of 60 %.

Keywords

Main Subjects


  1. Dick JS, Carl Hanser Verlag (2001) Compounding and Testing for Performance. In: Rubber technology, chapter 6
  2. Hanifpour A, Bahri-Laleh N, Nekoomanesh- Haghighi M, Mirmohammadi SA (2016) Poly1- hexene: New impact modifier in HIPS technology. J Appl Polym Sci 133: 8508
  3. Hanifpour A, Bahri-Lale N, Nekomanesh Haghighi M, Karimi M (2016) Study on unsaturated structure and tacticity of poly1- hexene and new copolymer of 1-hexene/5- hexene-1-ol prepared by metallocene catalyst. J Organomet Chem 819: 103–108
  4. 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 App Polym Sci 123: 2526-2533
  5. Bahri-Laleh N, Seifali Abbas-Abadi 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- 1786
  6. Bahri-Laleh N, Nekoomanesh-Haghighi M, Mirmohammadi SA (2012) A DFT study on the effect of hydrogen in ethylene and propylene polymerization using a Ti-based heterogeneous Ziegler–Natta catalyst. J Organomet Chem 719: 74-79
  7. Bahri-Laleh N, Poater A, Cavallo L, Mirmohammadi SA (2014) Exploring the mechanism of Grignard metathesis polymerization of 3-alkylthiophenes. Dalton Trans 43: 15143- 15150
  8. Hakim S, Nekoomanesh M, Shahrokhinia A (2015) The effect of mixed and individual silane external donors on the stereo-defect distribution, active sites and properties of polypropylene synthesized with fourth generation Ziegler-Natta catalyst. Polym Sci Ser-A 57: 573-580
  9. Kissin YV, Rishina LA (2008) Kinetics of propylene and ethylene polymerization reactions with heterogeneous ziegler-Natta catalysts: Recent results. Polym Sci Ser A 50: 1101-1121
  10. Novokshonova LA, Meshkova IN, Ushakova TM, Kudinova OI, Krasheninnikov VG (2008) Immobilized organometallic catalysts in the catalytic polymerization of olefins. Polym Sci Ser A 50: 1136-1150
  11. Dandge DK, Heller JP, Lien C, Wilson KV (1986) Kinetics of 1-hexene polymerization. J Appl Polym Sci 32: 5373-5384
  12. Kothandaraman H, Devi MS (1994) Kinetics of polymerization of 1-octene with MgCI2-supported TiCI4 catalysts. J Polym Sci Pol Chem 32: 1283- 1294
  13. Jiang X, Wang H, Tian X, Yang Y, 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: 259-266
  14. Li L, Wang Q (2004) Synthesis of polyethylene with bimodal molecular weight distribution by supported iron-based catalyst. J Polym Sci Pol Chem 42: 5662
  15. Sun J, Zhang H, Liu X, Xiao X, Lin F (2006) Ethylene polymerization by novel 4,4′-bis(methylene)biphenylene bridged homo-dinuclear titanocene and zirconocene combined with MAO. Eur Polym J 42: 1259
  16. Kissin YV, Liu X, Pollick DJ, Brungard NL, Chang M (2008) Ziegler-Natta catalysts for propylene polymerization: Chemistry of reactions leading to the formation of active centers. J Mol Catal A-Chem 287: 45-52
  17. Garoff T, Leinonen T (1996) Mn doping of the Ziegler-Natta PP catalyst support material. J Mol Catal A-Chem 104: 205-212
  18. Fregonese D, Bresadola S (1999) Catalytic systems supported on MgCl2 doped with ZnCl2 for olefin polymerization. J Mol Catal A-Chem 145: 265-271
  19. Bazvand R, Bahri-Laleh N, Nekoomanesh- Haghighi M, Abedini H (2015) Highly efficient FeCl3 doped Mg(OEt)2/TiCl4-based Ziegler– Natta catalysts for ethylene polymerization. Des Monomers Polym 18: 599-610
  20. Chen B, Zhang Q-F, Zhao L-P, Zhang X-Q, Zhang H-X (2013) Preparation and properties of isotactic polypropylene obtained from MgCl2- supported TiCl4 catalyst bearing bifunctional internal donor. Polym Bull 70: 2793-2800
  21. Chadwick JC, Morini G, Balbontin G, Camurati I, Heere JJR, Mingozzi I, Testoni F (2001) Effects of internal and external donors on the regio- and stereoselectivity of active species in MgCl2- supported catalysts for propene polymerization. Macromol Chem Phys 202: 1995-2002
  22. Hadian N, Hakim S, Nekoomanesh-Haghighi M, bahri-Laleh N (2014) Storage time effect on dynamic structure of MgCl2.nEtOH adducts in heterogeneous Ziegler-Natta catalysts. Polyolefins J 1: 33-41
  23. Rahbar A, Nekoomanesh-Haghighi M, Bahri- Laleh N, Abedini H (2015) Effect of water on the supported Ziegler–Natta catalysts: Optimization of the operating conditions by response surface methodology. Catal Lett: 1-10
  24. Nouri-Ahangarani F, Bahri-Laleh N, Nekomanesh-Haghighi M, Karbalaei M (2016) Synthesis of highly isotactic poly1-hexene using Fe-doped Mg(OEt)2/TiCl4/ED Ziegler-Natta catalytic system. Des Monomers Polym 19: 394- 405
  25. Noto DV, Bresadola S (1996) New synthesis of a highly active delta-MgCl2 for MgCl2/TiCl4/AlEt3 catalytic systems. Macromol Chem Phys 197: 3827-3835
  26. Sobota P (2004) Metal-assembled compounds: Precursors of polymerization catalysts and new materials. Coord Chem Rev 248: 1047-1060
  27. Thushara KS, Gnanakumar ES, Mathew R, Jha RK, Ajithkumar TG, Rajamohanan PR, Sarma K, Padmanabhan S, Bhaduri S, Gopinath CS (2011) Toward an understanding of the molecular level properties of Ziegler-Natta catalyst support with and without the internal electron donor. J Phys Chem C 115: 1952-1960
  28. Tewell CR, Malizia F, Ager JW, Somorjai GA (2002) An ultraviolet-raman spectroscopic investigation of magnesium chloride-ethanol solids with a 0.47 to 6 molar ratio of C2H5OH to MgCl2. J Phys Chem B 106: 2946-2949
  29. Kumawat J, Kumar Gupta V, Vanka K (2014) The nature of the active site in Ziegler–Natta olefin polymerization catalysis systems – A computational investigation. Eur J Inorg Chem 2014: 5063-5076
  30. Cui N, Ke Y, Li H, Zhang Z, Guo C, Lv z, Hu Y(2006) Effect of diether as internal donor on MgCl2-supported Ziegler–Natta catalyst for propylene polymerization. J Appl Polym Sci 99: 1399 –1404
  31. Kaur S, Naik DG, Singh G, Patil HR, Kothari AV, Gupta VK (2010) Poly(1-octene) synthesis using high performance supported titanium catalysts. J Appl Polym Sci 115: 229-236
  32. Jiang X, Tian X, Fan Z, Fang K, Fu Z, Xu J, wang Q (2007) Control of the molecular weight distribution (MWD) and tacticity of 1-hexene polymerization catalyzed by TiCl4/MgCl2-NaCl/ TEA catalysis system. J Mol Catal 72-76
  33. Vasilenko IV, Kostjuk SV (2006) The influence of cocatalysts on 1-hexene polymerization with various supported magnesium - titanium catalysts. Polym Bull 57: 129-138
  34. Asakura T, Demura M, Nishiyama Y (1991) Carbon-13 NMR spectral assignment of five polyolefins determined from the chemical shift calculation and the polymerization mechanism. Macromolecules 24: 2334-2340
  35. Galland GB, Da Silva LF, Nicolini A (2005) Tacticity of poly-α-olefins from poly-1-hexene to poly-1-octadecene. J Polym Sci Pol Chem 43: 4744-4753
  36. Jiang X, Fan Z-Q (2004) Stydy on 1-hexene polymerization based on Ziegler-Natta catalysts with doped support. Chinese J Polym Sci 22: 305- 308
  37. Xiao A, Wang L, Liu Q, Yu H, Dong X (2008) Synthesis of low isotactic polypropylene using MgCl2/AlCl3supported Ziegler–Natta catalysts prepared using the one-pot milling method. Des Monomers Polym 11: 139-145
  38. Busico V, Corradini P, De Martino L, Proto A, Savino V, Albizzati E (1985) Polymerization of propene in the presence of MgCl -supported Ziegler-Natta catalysts, 1. The role of ethyl benzoate as "internal"and "external" base. Makromol Chem 186: 1279-1288
  39. Chen Y-P, Fan Z-Q, Liao J-H, Liao S-Q (2006) Molecular weight distribution of polyethylene catalyzed by Ziegler–Natta catalyst supported on MgCl2 doped with AlCl3. J Appl Polym Sci 102: 1768-1772
  40. Mehdipour-Ataei S, Amirshaghaghi A, Bahri N (2006) Structure–property relations in heat resistant polyesters with built-in ether and imide units. Eur Polym J 42: 2646-2654
  41. Mehdipour-Ataei S, Bahri-Laleh N (2008) Preparation and characterization of thermally stable poly(amide-urea)s functionalized with anthraquinone chromophore. Polym Adv Technol 19: 291-298
  42. Mehdipour–Ataei S, Babanzadeh S, Bahri-Laleh N (2006) Novel thermally stable poly (sulfone ether ester amide)s with improved solubility. E-Polymers 6: 599-609
  43. Liu F, Gao H, Hu Z, Hu H, Zhu F, Wu Q (2012) Poly(1-hexene) with long methylene sequences and controlled branches obtained by a thermostable α-diimine nickel catalyst with bulky camphyl backbone. J Polym Sci Pol Chem 50: 3859-3866