Issue
Korean Journal of Chemical Engineering,
Vol.21, No.1, 110-115, 2004
Recycling of Methylaluminoxane (MAO) Cocatalyst in Ethylene Polymerization with Supported Metallocene Catalyst
The economy of the metallocene catalyst system in olefin polymerization depends more on the cost of methylaluminoxane (MAO) cocatalyst rather than on the catalyst cost since high ratio of cocatalyst to catalyst is required to have sufficient activity. The conditions to minimize the consumption of MAO have been studied for the ethylene polymerization with supported metallocene catalyst. By introducing the prepolymerization step, in which the supported metallocene catalyst is activated at high MAO concentration before polymerization, the MAO could be recovered after the prepolymerization and recycled repeatedly for the subsequent activation with marginal decrease in activity. No extra MAO was needed during the main polymerization. The addition of small amount of MAO or less expensive alkylaluminum at each recycle step kept the catalyst activity to the initial level. It compensates the MAO losses occurring both by the incomplete decantation of MAO solution and by the reaction with metallocene complex or impurities. As a result, the actual consumption ratio of Al/Zr in moles in commercial applications could be reduced to about 30 without sacrificing the activity. This value is significantly low considering that conventionally an Al/Zr ratio of 1,000 is required for sufficient activity.
[References]
  1. Brockmeier NF, "Polypropylene Reinvented-Cost of Using Metallocene Catalysts, Metallocene Catalyzed Polymers-Materials, Properties, Processing and Markets, Benedikt, G.M. and Goodall, B.L., eds., Plastics Design Library, Norwich, NY, 1998
  2. Chien JCW, Wang BP, J. Polym. Sci. A: Polym. Chem., 26, 3089, 1988
  3. Chien JCW, Sugimoto R, J. Polym. Sci. A: Polym. Chem., 29, 459, 1991
  4. Cho HS, Choi KH, Choi DJ, Lee WY, Korean J. Chem. Eng., 17(2), 205, 2000
  5. Chung JS, Tairova G, Zhang Y, Hsu JC, McAuley KB, Bacon DW, Korean J. Chem. Eng., 19(4), 597, 2002
  6. Coevoet D, Cramail H, Defieux A, Macromol. Chem. Phys., 199, 1451, 1998
  7. dos Santos JHZ, Da Rosa MB, Krug C, Stedile FC, Haag MC, Dupont J, Forte MD, J. Polym. Sci. A: Polym. Chem., 37(13), 1987, 1999
  8. Haag MC, Krug C, Dupont J, deGalland GB, dosSantos JHZ, Uozumi T, Sano T, Soga K, J. Mol. Catal. A-Chem., 169, 275, 2001
  9. Han TK, Seo TS, Choi HK, Woo SI, Korean J. Chem. Eng., 16(2), 156, 1999
  10. Herfert N, Fink G, Makromol. Chem., 193, 1359, 1992
  11. Hlatky GG, Chem. Rev., 100(4), 1347, 2000
  12. Jeong BG, Nam DW, Hong SD, Lee SG, Park YW, Song KH, Korean J. Chem. Eng., 20(1), 22, 2003
  13. Khrushch NE, Bravaya NM, J. Mol. Catal. A-Chem., 156, 69, 2000
  14. Lee BY, Oh JS, Macromolecules, 33(9), 3194, 2000
  15. Panin AN, Dzhabieva ZM, Nedorezova PM, Tsvetkova VI, Saratovskikh SL, Babkina ON, Bravaya NM, J. Polym. Sci. A: Polym. Chem., 39(11), 1915, 2001
  16. Pedeutour JN, Radhakrishnan K, Cramail H, Deffieux A, Macromol. Rapid Commun., 22, 1095, 2001
  17. Ribeiro MR, Deffieux A, Portela MF, Ind. Eng. Chem. Res., 36(4), 1224, 1997
  18. Oh JS, Lee BY, Oum YH, Park TH, "Method for Olefin Polymerization with Recycling of Cocatalyst," U.S. Patent, 6,340,728, 2002
  19. Scheirs J, Kaminsky W, "Metallocene-Based Polyolefins," Vol. 1 and 2, Wiley, Chichester, 2000
  20. Sullivan JM, "Economic Factors for the Production of Metallocene and Perfluorinated Boron Catalysts," Metallocene Catalyzed Polymers-Materials, Properties, Processing and Markets, Benedikt, G.M. and Goodall, B.L., eds., Plastics Design Library, Norwich, NY, 1998
  21. Togni A, Halterman RL, "Metallocene Synthesis Reactivity Applications," Vol. 1 and 2, Wiley/VCH, Weinheim, 1998