Polymer Bulletin

, Volume 66, Issue 5, pp 627–635 | Cite as

Preparation of ultra high molecular weight polyethylene with MgCl2/TiCl4 catalyst: effect of internal and external donor on molecular weight and molecular weight distribution

  • He-xin Zhang
  • Young-jun Shin
  • Dong-ho Lee
  • Keun-Byoung YoonEmail author
Original Paper


Ultra high molecular weight polyethylene (UHMWPE) was prepared by using MgCl2-supported TiCl4 catalyst in conjunction with triethylaluminium (TEA) cocatalyst. The effects of internal and external donor on polydispersity index (PDI) of UHMWPE were investigated. The catalyst activity with various kinds of internal donor decreased in the following order: none > succinate > phthalate > diether, while the catalyst activity was less influenced by the structure of external donor. The PDI of UHMWPE was examined by using gel permeation chromatography (GPC) analysis and/or rheometry measurements. The PDI obtained by rheometer was matched with the results obtained by GPC within an error of max. 20%. The highest molecular weight and PDI of UHMWPE were obtained by the catalyst of succinate as internal donor. It was also observed that the molecular weight and PDI of UHMWPE were less affected by the introduction of external donor.


UHMWPE Internal donor External donor Molecular weight distribution 


  1. 1.
    Cohen Y, Rein DM, Vaykhansky L (1997) A novel composite based on ultra-high-molecular-weight polyethylene. Compos Sci Technol 57:1149–1154CrossRefGoogle Scholar
  2. 2.
    Galetz MC, Blap T, Ruckdaschel H, Sandler JKW, Altstadt V, Glatzel U (2007) Carbon nanofibre-reinforced ultra high molecular weight polyethylene for tribological applications. J Appl Polym Sci 104:4173–4181CrossRefGoogle Scholar
  3. 3.
    Deng M, Uhrich KE (1998) Analysis of thermal properties of polymeric biomaterials. I. Ultra-high-molecular-weight polyethylene. J Appl Polym Sci 68:1353–1361CrossRefGoogle Scholar
  4. 4.
    Xie XL, Tang CY, Chan KYY, Wu XC, Tsui CP, Cheung CY (2003) Wear performance of ultra high molecular weight polyethylene/quartz composites. Biomaterials 24:1889–1896CrossRefGoogle Scholar
  5. 5.
    Ingrah JH, Stone M, Fisher J, Ingham E (2004) The influence of molecular weight, crosslinking and counterface roughness on TNF-alpha production by macrophages in response to ultra high molecular weight polyethylene particles. Biomaterials 25:3511–3522CrossRefGoogle Scholar
  6. 6.
    Park HJ, Kwak SY, Kwak SJ (2005) Wear-resistant ultra high molecular weight polyethylene/zirconia composites prepared by in situ Ziegler-Natta polymerization. Macromol Chem Phys 206:945–950CrossRefGoogle Scholar
  7. 7.
    Xiong D, Gao Z, Jin Z (2007) Friction and wear properties of UHMWPE against ion implanted titanium alloy. Surf Coat Technol 201:6847–6850CrossRefGoogle Scholar
  8. 8.
    Lewis G (2001) Properties of crosslinked ultra-high-molecular-weight polyethylene. Biomaterials 22:371–401CrossRefGoogle Scholar
  9. 9.
    Kashiwa N (2004) The discovery and progress of MgCl2-supported TiCl4 catalysts. J Polym Sci Part A Polym Chem 42:1–8CrossRefGoogle Scholar
  10. 10.
    Soga K, Shiono T, Doi Y (1988) Influence of internal and external donors on activity and stereospecificity of Ziegler-Natta catalysts. Makromol Chem 189:1531–1541CrossRefGoogle Scholar
  11. 11.
    Sacchi MC, Forlini F, Tritto I, Locatelli P, Morini G, Noristi L, Albizzati E (1996) Polymerization stereochemistry with Ziegler–Natta catalysts containing dialkylpropane diethers: a tool for understanding internal/external donor relationships. Macromolecules 29:3341–3345CrossRefGoogle Scholar
  12. 12.
    Cui N, Ke Y, Li H, Zhang Z, Guo C, Lv Z, Hu Y (2005) Effect of diether as internal donor on MgCl2-supported Ziegler-Natta catalyst for propylene polymerization. J Appl Polym Sci 99:1399–1404CrossRefGoogle Scholar
  13. 13.
    Forte MC, Coutinho FMB (1996) The influence of catalyst system and polymerization conditions on polypropylene properties. Eur Polym J 32:605–611CrossRefGoogle Scholar
  14. 14.
    Proto A, Oliva L, Pellecchia C, Sivak AJ, Cullo LA (1990) Isotactic-specific polymerization of propene with supported catalysts in the presence of different modifiers. Macromolecules 23:2904–2907CrossRefGoogle Scholar
  15. 15.
    Seppala JV, Harkonen M, Luciani L (1989) Effect of the structure of external alkoxysilane donors on the polymerization of propene with high activity Ziegler-Natta catalysts. Makromol Chem 190:2535–2550CrossRefGoogle Scholar
  16. 16.
    Sacchi MC, Forlini F, Tritto I, Mendichi R, Zannoni G, Noristi L (1992) Activation effect of alkoxysilanes as external donors in magnesium chloride-supported Ziegler-Natta catalysts. Macromolecules 25:5914–5918CrossRefGoogle Scholar
  17. 17.
    Hindryckx F, Dubois P, Jerome R, Marti MG (1998) Ethylene polymerization by a high activity MgCl2 supported Ti catalyst in the presence of hydrogen and/or 1-octene. Polymer 39:621–629CrossRefGoogle Scholar
  18. 18.
    Hasebe K, Fujiwara A, Nozaki T, Miyamoto K (2007) Ultra high molecular weight ethene copolymers from metallocene and Ziegler catalysts. Macromol Symp 260:161–164CrossRefGoogle Scholar
  19. 19.
    Tuminello WH (1986) Molecular weight and molecular weight distribution from dynamic measurements of polymer melts. Polym Eng Sci 26:1339–1347CrossRefGoogle Scholar
  20. 20.
    Tuminello WH, Treat TA, English AD (1988) Poly(tetrafluoroethylene): molecular weight distributions and chain stiffness. Macromolecules 21:2606–2610CrossRefGoogle Scholar
  21. 21.
    Soga K, Shiono T (1997) Ziegler-Natta catalysts for olefin polymerizations. Prog Polym Sci 22:1503–1546CrossRefGoogle Scholar
  22. 22.
    Lee DH, Jeong YT (1993) Propene polymerization with Mg(OEt)2-supported TiCl4 catalyst—4. Effects of hydrogen. Eur Polym J 29:883–888CrossRefGoogle Scholar
  23. 23.
    Kang KK, Kim KS, Lee DH, Jeong YT (2001) Propylene polymerization by using TiCl4 catalyst supported on solvent-activated Mg(OEt)2. J Appl Polym Sci 81:460–467CrossRefGoogle Scholar
  24. 24.
    Shiono T, Hagihara H, Ikeda T, Soga K (1997) Control of molecular weight distribution of isotactic polypropylene obtained by a MgCl2-supported TiCl4 catalyst. Polymer 38:6409–6411CrossRefGoogle Scholar
  25. 25.
    Soga K, Shiono T, Doi Y (1983) Effect of ethyl benzoate on the copolymerization of ethylene with higher α-olefins over TiCl4/MgCl2 catalytic systems. Polym. Bull. 10:168–174CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2010

Authors and Affiliations

  • He-xin Zhang
    • 1
  • Young-jun Shin
    • 2
  • Dong-ho Lee
    • 1
  • Keun-Byoung Yoon
    • 1
    Email author
  1. 1.Department of Polymer Science and EngineeringKyungpook National UniversityDaeguKorea
  2. 2.R&D CenterKorea Petrochemical Ind., Co., Ltd.UlsanKorea

Personalised recommendations