Role of dispersion state of ti species in deactivation of MgCl2-supported Ziegler-Natta catalysts

Toshiaki Taniike; Toru Wada; Iku Kouzai; Shougo Takahashi; Minoru Terano

Macromolecular Research, Vol.18, No.9, 839-844, September, 2010

DOI10.1007/s13233-010-0914-1 Export Citation

Role of dispersion state of ti species in deactivation of MgCl2-supported Ziegler-Natta catalysts

Toshiaki Taniike, Toru Wada, Iku Kouzai, Shougo Takahashi, and Minoru Terano^†

School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi, Ishikawa, 923-1292, Japan

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The deactivation behaviors of TiCl3/MgCl2 model catalysts with molecularly dispersed TiCl3 were investigated to clarify the role of the dispersion state of the Ti species in the deactivation of MgCl2-supported Ziegler-Natta (ZN) catalysts for propylene and ethylene polymerization. The propylene and ethylene polymerization activities of clustered Ti species supported on MgCl2 were approximately one tenth of those of isolated Ti species, which is indicative of the significance of the aggregation of Ti species in the deactivation of ZN catalysts for olefin polymerization. Moreover, the time-course depression of monomer consumption for the clustered Ti species was slower than that for the isolated Ti species in propylene polymerization, whereas the dispersion state barely affected the depression rate in ethylene polymerization. The reduction rate of the Ti species was concluded to be important for the time-course depression of propylene consumption, whereas ethylene polymerization was insensitive to the oxidation state of the Ti species.

Keywords:role of dispersion state of Ti species;deactivation;MgCl2-supported Ziegler-Natta catalysts

[References]

Albizzati E, Giannini U, Collina G, Noristi L, Resconi L, in Propylene Handbook, Moore EP, Ed., Hanser, New York, 1996, Chapter 2.
Boor J, in Ziegler-Natta Catalysts and Polymerization, Academic Press, New York, 1979, Chapter 8 and 18.
Keii T, Makromol. Chem., 183, 2285 (1982)
Soga K, Chen S, Ohnishi R, Polym. Bull., 8, 473 (1982)
Kashiwa N, Yoshitake J, Makromol. Chem., 185, 1133 (1984)
Albizzati E, Giannini U, Balbontin G, Camurati I, Chadwick JC, Dallocco T, Dubitsky Y, Calimberti M, Morini G, Maldotti A, J. Polym. Sci. A: Polym. Chem., 35(13), 2645 (1997)
Chien JC, Wu JC, J. Polym. Sci., 20, 2461 (1982)
Zakharov VA, Makhtarulin SI, Poluboyarov VA, Anufrienko VF, Makromol. Chem., 185, 1781 (1984)
Sergei SA, Poluboyyarov VA, Zakharov VA, Anufrienko VF, Bukatov GD, Makromol. Chem., 186, 243 (1985)
Brant P, Speca AN, Macromolecules, 20, 2740 (1987)
Tregubov AA, Zakharov VA, Mikenas TB, J. Polym. Sci. A: Polym. Chem., 47(23), 6362 (2009)
Tait PJT, Zohuri GH, Kells AM, Mckenzie ID, in Ziegler Catalysts, Fink G, Mulhaupt R, Bruntzunger HH, Eds., Springer-Verlag, Berlin, p. 343.
Dashti A, Ramazani A, Hiraoka Y, Kim SY, Taniike T, Terano M, Polym. Int., 58, 40 (2009)
Soga K, Terano M, Makromol. Chem., 182, 2439 (1981)
Kouzai I, Liu B, Wada T, Terano M, Macromol. React. Eng., 1, 160 (2007)
Wada T, Taniike T, Kouzai I, Takahashi S, Terano M, Macromol. Rapid Commun., 30(11), 887 (2009)
Ludlu DB, Anderson AW, Ashby CE, J. Am. Chem. Soc., 80, 1380 (1958)
Nejad MH, Ferrari P, Pennini G, Cecchin G, J. Appl. Polym. Sci., 108(5), 3388 (2008)

[1] Albizzati E, Giannini U, Collina G, Noristi L, Resconi L, in Propylene Handbook, Moore EP, Ed., Hanser, New York, 1996, Chapter 2.

[2] Boor J, in Ziegler-Natta Catalysts and Polymerization, Academic Press, New York, 1979, Chapter 8 and 18.

[3] Keii T, Makromol. Chem., 183, 2285 (1982)

[4] Soga K, Chen S, Ohnishi R, Polym. Bull., 8, 473 (1982)

[5] Kashiwa N, Yoshitake J, Makromol. Chem., 185, 1133 (1984)

[6] Albizzati E, Giannini U, Balbontin G, Camurati I, Chadwick JC, Dallocco T, Dubitsky Y, Calimberti M, Morini G, Maldotti A, J. Polym. Sci. A: Polym. Chem., 35(13), 2645 (1997)

[7] Chien JC, Wu JC, J. Polym. Sci., 20, 2461 (1982)

[8] Zakharov VA, Makhtarulin SI, Poluboyarov VA, Anufrienko VF, Makromol. Chem., 185, 1781 (1984)

[9] Sergei SA, Poluboyyarov VA, Zakharov VA, Anufrienko VF, Bukatov GD, Makromol. Chem., 186, 243 (1985)

[10] Brant P, Speca AN, Macromolecules, 20, 2740 (1987)

[11] Tregubov AA, Zakharov VA, Mikenas TB, J. Polym. Sci. A: Polym. Chem., 47(23), 6362 (2009)

[12] Tait PJT, Zohuri GH, Kells AM, Mckenzie ID, in Ziegler Catalysts, Fink G, Mulhaupt R, Bruntzunger HH, Eds., Springer-Verlag, Berlin, p. 343.

[13] Dashti A, Ramazani A, Hiraoka Y, Kim SY, Taniike T, Terano M, Polym. Int., 58, 40 (2009)

[14] Soga K, Terano M, Makromol. Chem., 182, 2439 (1981)

[15] Kouzai I, Liu B, Wada T, Terano M, Macromol. React. Eng., 1, 160 (2007)

[16] Wada T, Taniike T, Kouzai I, Takahashi S, Terano M, Macromol. Rapid Commun., 30(11), 887 (2009)

[17] Ludlu DB, Anderson AW, Ashby CE, J. Am. Chem. Soc., 80, 1380 (1958)

[18] Nejad MH, Ferrari P, Pennini G, Cecchin G, J. Appl. Polym. Sci., 108(5), 3388 (2008)