Polyolefins Journal
With the collaboration of Iran Polymer Society

Synthesis of high molecular weight polyethylene using FI catalyst

Document Type : Original research

Authors

G. Hossein Zohuri 1
Saman Damavandi 2
Saeid Ahmadjo 3
Reza sandaroos 4
Mohammad A. Shamekhi 2

1 Department of Chemistry, Faculty of Science, Ferdowsi University of Mashhad, Mashhad, Iran

2 Department of Chemistry, Sarvestan Branch, Islamic Azad University, Fars, Iran

3 Department of Catalyst, Iran Polymer and Petrochemical Institute, Tehran, Iran

4 Department of Chemistry, Faculty of Science, University of Birjand, Birjand, Iran

https://doi.org/10.22063/poj.2014.925
Abstract
A FI Zr-based catalyst of bis[N-(3,5-dicumylsalicylidene)-2′,6′­diisopropylanilinato]zirconium(IV) dichloride was prepared and used for polymerization of ethylene. The effects of reaction conditions on the polymerization were examined in detail. The increase in ethylene pressure and rise in polymerization temperature up to 35 oC were favorable for catalyst/MAO to raise the catalytic activity as well as the viscosity-average molecular weight (Mv) of polyethylene. The activity of the catalyst was linearly increased with increasing MAO concentration and no optimum activity was observed in the range studied. Although introduction of the bulky cumyl and 2′,6′-diisopropyl alkyl substitution groups on ortho positions to the phenoxy-oxygen and on phenyl ring on the N, respectively enhanced the viscosity average molecular weight (Mv) of the obtained polymer strongly, diminished the activity of the catalyst. Neither the activity of the catalyst nor the (Mv) of the obtained polymer were sensitive to hydrogen concentration. However, higher amount of hydrogen could slightly increase the activity of the catalyst. The (Mv) of polyethylene ranged from 2.14×106 to 2.77×106 at the monomer pressure of 3 and 5 bar respectively which are much higher than that of the reported FI Zr-based catalysts.

Keywords

FI Catalyst
high molecular weight
polyethylene
Ethylene polymerization
Subjects
  1. Sandaroos R, Damavandi S, Goldani MT (2012) Preparation of new FI-type catalyst for polymerization of ethylene. e-Polymers 060:1-10
  2. Gibson VC, Spitzmesser SK (2003) Advances in non-metallocene olefin polymerization catalysis Chem Rev 103:283-316
  3. Wang C, Friedrich S, Younkin TR (1998) Neutral nickel (II)-based catalysts for ethylene polymerization. Organometallics 17:3149-3151
  4. Carlini C, Martinelli M, Raspolli GAM, Sbrana G (2002) Copolymerization of ethylene with methyl methacrylate by Ziegler-Natta-type catalysts based on nickel salicylaldiminate/ methylalumoxane systems. Macromol Chem Phys 203:1606–1613
  5. Nakayama Y, Kawai K, Fujita T (2010) FI Catalysts: unique olefin polymerization catalysis for formation of value-added olefin-based materials. J Jap Petrol Inst 53:111-129
  6. Saito J, Mitani M, Onda M, Mohri J, Ishii S, Yoshida Y, Nakano T, Tanaka H, Matsugi T, Kojoh S, Kashiwa N, Fujita T (2001) Microstructure of highly syndiotactic “Living” poly(propylene)s produced from a titanium complex with chelating fluorine-containing phenoxyimine ligands Macromol Rapid Commun 22:1072-1075
  7. Saito J, Mitani M, Mohri J, Ishii S, Yoshida Y, Matsugi T, Kojoh S, Kashiwa N, Fujita T (2001) Highly syndiospecific living polymerization of propylene using a titanium complex having two phenoxy-imine chelate ligands. Chem Lett 576– 582
  8. Nakayama Y, Saito J, Bando H, Fujita T (2005) Propylene polymerization behavior of fluorinated bis(phenoxy-imine) Ti complexes with an MgCl2- based compound (MgCl2 supported Ti-based catalysts). Macromol Chem Phys 206:1847–1852
  9. Ishii S, Saito J, Mitani M, Mohri J, Natsukawa N, Tohi Y, Matsui S, Kashiwa N, Fujita T (2002) Highly active ethylene polymerization catalysts based on titanium complexes having two phenoxy-imine chelate ligands. J Mol Catal A Chem 179:11- 16
  10. Mitani M, Mohri J, Yoshida Y, Saito J, Ishii S, Tsuru K, Matsui S, Furuyama R, Nakano T, Tanaka H, Kojoh S, Matsugi T, Kashiwa N, Fujita T (2002) Living polymerization of ethylene catalyzed by titanium complexes having fluorine-containing phenoxy-imine chelate ligands. J Am Chem Soc 124:3327-3336
  11. Kurtz SM (1985) Ultra high molecular weight polyethylene. In: Biomaterials Handbook, Elsevier, 31-41
  12. Kurtz SM, Gsell RA, Martell J (Eds). STP1445: Crosslinked and thermally treated ultra-high molecular weight polyethylene for joint replacements. Conshohocken: ASTM International, 2004. Doi: 10.1520/STP1445-EB
  13. Keller A, Hikosaka M, Toda A, Rastogi S, Barham PJ, Gooldbeck-Wood G (1994) An approach to the formation and growth of new phases with application to polymer crystallization: effect of finite size, metastability, and Ostwald's rule of stages. J Mater Sci 29:2579-2604
  14. Matsui S, Fujita T (2001) FI Catalysts: super active new ethylene polymerization catalysts. Catal Today 66:63-73
  15. Matsui S, Tohi Y, Mitani M, Saito J, Makio M, Tanaka H, Nitabaru M, Nakano K, Fujita T (1999) New bis(salicylaldiminato) titanium complexes for ethylene polymerization Chem Lett 28:1065
  16. Saito J, Mitani M, Mohri J, Ishii S, Yoshida Y, Matsugi T, Kojoh S, Kashiwa N, Fujita T(2001) Highly syndiospecific living polymerization of propylene using a titanium complex having two phenoxy-imine chelate ligands. Chem Lett 576, 582
  17. Coates GW, Tian J, Hustad PD (2003) Bis(salicylaldiminato)titanium complex catalysts, highly syndiotactic polypropylene by a chain-end control mechanism, block copolymers containing this. US Patent 6562930
  18. Zohuri GH, Damavandi S, Sandaroos R, Ahmadjo S (2011) Ethylene polymerization using fluorinated FI Zr-based catalyst. Polym Bull 66:1051–1062
  19. Damavandi S, Sandaroos R, Shamekhi MA (2012) Synthesis and application of FI catalyst for ethylene polymerization. J Macromol Sci, Part A: Pure Appl Chem 49:339–347
  20. Zohuri G H, Damavandi S, Dianat E, Sandaroos R, Ahmadjo S (2011) Late transition metal catalyst based on cobalt for polymerization of ethylene Int J Polym Mater 60:776–78621. 
  21. Damavandi S, Galland GB, Zohuri GH, Sandaroos R (2011) FI Zr-type catalysts for ethylene polymerization. J Polym Res 18:1059–1065
  22. Chiang R (1959) Comments on intrinsic viscosity– weight-average molecular weight relationships for polyethylene. J Polym Sci 36:91-103
  23. Justino J, Dias AR, Ascenso J, Marcues MM, Tait PJT (1997) Polymerization of ethylene using metallocene and aluminoxane systems. Polym Int 44:407–412
  24. Lancaster SJ, O’Hara SM, Bochmann M (1999) Heterogenised MAO-free metallocene catalysts. In: Metal organic catalysts for synthesis and polymerization. 413-425
  25. Furuyama R, Saito J, Ishii SI, Mitani M, Matsui S, Tohi Y, Makio H, Matsukawa N, Tanaka H, Fujita T (2003) J Mol Catal A: Chem 200:31-37
  26. Ahmadjo S, Zohuri GH, Damavandi S, Sandaroos R (2010) Comparative ethylene polymerization using FI-like zirconium based catalysts. Reac Kinet Mech Cat 101:429–442

  • Receive Date 29 December 2012
  • Revise Date 23 October 2013
  • Accept Date 30 October 2013
  • First Publish Date 01 January 2014

Article View 10,190
PDF Download 5,276

Home

Editorial Board

Publication Ethics

Submit Manuscript

Contact Us