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Supported Catalysts for Polypropylene: Aluminum Alkyl-Ester Chemistry

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Coordination Polymerization

Part of the book series: Polymer Science and Technology ((POLS,volume 19))

Synopsis

The reactions of aluminum alkyl cocatalysts with the ethyl benzoate (EB) component of MgCl2 supported TiCl4 catalysts have a strong influence on both activity and stereospecificity. NMR investigations show that AlEt3 alkylates ethyl benzoate by the following reaction: PhCO2Et + 3 AlEt3 → 1/2 (Et2AlOEt)2 + Et3Al·Et2AlOCEt2Ph. The rate of ethyl benzoate consumption decreases with lower Al/PhCO2Et ratios. Atmospheric pressure polymerization studies reveal that the interaction of ethyl benzoate with the catalyst is responsible for achieving high isotacticity as measured by heptane insolubles (% HI). The aluminum alkoxide products from the alkylation reaction increase HI indirectly by complexing AlEt3, lowering the free [AlEt3] and the AlEt3/PhCO2Et ratio. However, lower free [AlEt3] also reduces polymerization rate. The introduction of steric bulk into the aluminum alkyl component minimizes the ester alkylation reaction while maintaining catalyst activity. Two types of cocatalysts have been found which give significantly better catalyst performance than the AlEt3 cocatalyst: (1) sterically hindered trialkyl aluminum cocatalysts, such as s-Bu2AlEt and t-Bu2AlEt and (2) certain aluminum dialkyl and diary1 amides such as Et2Al-2,2,6,6-tetramethylpiperidide and Et2AlNPh2.

Ethyl benzoate improves HI by inactivating the nonstereo- specific polymerization sites to a greater degree than the stereo- specific site. This has led to the finding that 2,2,6,6-tetra- methylpiperidine is highly selective in complexing the nonstereo- specific sites with minimal interaction toward stereospecific sites.

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References

  1. P. Pino, R. Mulhaupt, Angew, Chem. Int. Ed. Engl. 19, 857 (1980).

    Article  Google Scholar 

  2. K. Ziegler, Belg. Pat. 533,362. K. Ziegler, E. Holzkamp, H. Breil, H. Martin, Angew, Chem. 67, 541 (1955).

    Google Scholar 

  3. G. Natta, J. Polymer Sci. 16, 143 (1955).

    Article  CAS  Google Scholar 

  4. E. Tornqvist, C. W. Seelbach, A. W. Langer, Jr., (Exxon), U.S. Pat. 3,128,252 (1964). E. Tornqvist, A. W. Langer, Jr., (Exxon), U.S. Pat. 3, 032, 510 (1962).

    Google Scholar 

  5. Brit. Pat. 895,595 (1962) (Hoechst). K. K. G. Rust, A. G. M. Gumboldt, K. F. Horndler, S. Sommer, E. Heitzer (Hoechst, assigned to Hercules), U.S. Pat. 3, 058, 970 (1962).

    Google Scholar 

  6. J. P. Hermans, P. Henrioulle (Solvay), DBP 2,213,086 (1972), U.S. Pat, 4,210,738 (1980) and 4,210, 735 (1980).

    Google Scholar 

  7. M. Yokoyama, A. Yamada, S. Okosi, T. Katou, S. Yoshida, (Mitsubishi Petrochem.), U.S. Pat, 4,151, 111 (1979).

    Google Scholar 

  8. H. Ueno, N. Inaba, T. Makishima, K. Watanabe, S. Wada (Exxon) U.S. Pat. 4, 182, 691 (1980).

    Google Scholar 

  9. E. Tornqvist, Ann. N.Y. Acad. Sci, 155, 447 (1969).

    Google Scholar 

  10. W. A. Hewett, E. C. Shokal (Shell), U.S. Pat, 3, 238, 146 (1966).

    Google Scholar 

  11. A. Mayr, P. Galli, E. Susa, G. DiDrusco, E. Cischetti (Montecatini), Brit. Pat. 1, 286, 867 (1969).

    Google Scholar 

  12. N. Kashiwa, T. Tokuzumi, O. Fujimura, H. Fujimura (Mitsui Petrochem.), U.S. Pat. 3,642, 746 (1972).

    Google Scholar 

  13. P. Longi, U. Giannini, A. Cassata (Montecatini), Brit. Pat. I, 335, 887 (1973).

    Google Scholar 

  14. T. Mole and E. A. Jeffrey, Organoaluminum Compounds, Elsevier Publishing Company (1972), p. 302.

    Google Scholar 

  15. E. C. Ashby, J. Laemmle, and H. M. Neumann, J. Amer. Chem. Soc., 90, 5179 (1968).

    Article  CAS  Google Scholar 

  16. E. G. Hoffmann, Ann. Chem. 629, 104 (1960).

    CAS  Google Scholar 

  17. J. Smidt, M. P. Groenewege and H. de Vries, Recueil 81, 729(1962)

    Article  Google Scholar 

  18. E. A Jeffrey and T. Mole, Aust. J. Chem. 23, 715 (1970).

    Article  Google Scholar 

  19. For reactions of Ali-Bu and AlEt with ethyl benzoate see also D. Adenhaim and J. L. Namy, Tet Letters, 3011 (1972).

    Google Scholar 

  20. Y. Baba, Bull. Chem. Soc., Japan 41, 1022 (1968).

    Google Scholar 

  21. S. Pasynkiewicz and E. Sliwa, J. Organometal. Chem. 3, 121(1965)

    Google Scholar 

  22. A. W. Langer, Jr., Ann. N.Y. Acad. Sci. 295, 110 (1977).

    Article  CAS  Google Scholar 

  23. A. W. Langer, T. J. Burkhardt, J. J. Steger, unpublished results.

    Google Scholar 

  24. T. Mole, Australian J. Chem. 19, 373 (1966); G. E. Coates and J. G. aham, J. Chem. Soc., 233 (1963).

    Article  Google Scholar 

  25. M. S. Newman, J. Amer. Chem. Soc. 63, 2431 (1941).

    Article  CAS  Google Scholar 

  26. C. L. Frye, G. A. Vincent, G. L. Hauschildt. J. Amer. Chem. Soc. 88, 2727 (1966).

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Corporate Research Laboratories, Exxon Research and Engineering Company, Linden, New Jersey, 07036, USA

    Arthur W. Langer, Terry J. Burkhardt & John J. Steger

Authors
  1. Arthur W. Langer
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  2. Terry J. Burkhardt
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  3. John J. Steger
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Editor information

Editors and Affiliations

  1. University of Pennsylvania, Philadelphia, Pennsylvania, 19104, USA

    Charles C. Price (Benjamin Franklin Professor of Chemistry (Emeritus) (Benjamin Franklin Professor of Chemistry (Emeritus)

  2. Hercules Incorporated Research Center, Wilmington, Delaware, USA

    Edwin J. Vandenberg

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© 1983 Plenum Press, New York

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Langer, A.W., Burkhardt, T.J., Steger, J.J. (1983). Supported Catalysts for Polypropylene: Aluminum Alkyl-Ester Chemistry. In: Price, C.C., Vandenberg, E.J. (eds) Coordination Polymerization. Polymer Science and Technology, vol 19. Springer, Boston, MA. https://doi.org/10.1007/978-1-4613-3575-7_12

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  • DOI: https://doi.org/10.1007/978-1-4613-3575-7_12

  • Publisher Name: Springer, Boston, MA

  • Print ISBN: 978-1-4613-3577-1

  • Online ISBN: 978-1-4613-3575-7

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