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LLDPE with Exclusively Ethyl Branches by Tandem Catalysis with Single-Site Zr(IV)/Co(II) Catalysts

Abstract

Semicrystalline linear low density polyethylenes (LLDPEs) with exclusively ethyl branching (from 7 to 56 branches per 1,000 carbon atoms) were prepared from ethylene by homogeneous tandem catalytic systems comprising (imino)pyridine cobalt(II) dichlorides as oligomerization precursors, bis(cyclopentadienyl)zirconium(IV) dichloride as copolymerization precursor and methyaluminoxane as activator. The activity of the tandem systems was evaluated by varying either the molar fraction of the cobalt precursors or the ethylene pressure. The latter parameter was of crucial importance to control both the productivity and the extent of 1-butene incorporation. In particular, increasing the ethylene pressure from 2 bar to 4 bar changed the “comonomer effect” from positive to negative.

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References

  1. 1.

    Bianchini C, Miller H, Ciardelli F (2004) In: Ciardelli F, Penczek S (eds) Modification and blending of synthetic and natural macromolecules. Kluwer Academic Publishers, The Netherlands, pp 15–38

  2. 2.

    Komon ZJA, Bazan GC (2001) Macromol Rapid Commun 22:467

  3. 3.

    (a) Furlan LG, Kunrath FA, Mauler RS, de Souza RF, Casagrande OL Jr (2004) J Mol Catal A: Chem 214:207; (b) Kuhn MCA, da Silva JL, Casagrande ACA, Mauler RS, Casagrande OL Jr (2006) Macromol Chem Phys 207:827

  4. 4.

    Ye Z, AlObaidi F, Zhu S (2004) Macromol Rapid Commun 25:647

  5. 5.

    Sperber O, Kaminsky W (2003) Macromolecules 36:9014

  6. 6.

    Wang H, Ma Z, Ke Y, Hu Y (2003) Polym Int 52:1546

  7. 7.

    (a) Wang J, Li H, Guo N, Li L, Stern CL, Marks TJ (2004) Organometallics 23:5112; (b) Li L, Metz MV, Li H, Chen M-C, Marks TJ, Liable-Sands L, Rheingold AL (2002) J Am Chem Soc 124:12725; (c) Abramo GP, Li L, Marks TJ (2002) J Am Chem Soc 124:13966; (d) Li H, Li L, Schwartz DJ, Metz MV, Marks TJ, Liable-Sands L, Rheingold AL (2005) J Am Chem Soc 127:14756

  8. 8.

    (a) Komon ZJA, Diamond GM, Leclerc MK, Murphy V, Okazaki M, Bazan GC (2002) J Am Chem Soc 124:15280; (b) Galland GB, Quijada R, Rojas R, Bazan G, Komon ZJA (2002) Macromolecules 35:339; (c) Quijada R, Rojas R, Bazan G, Komon ZJA, Mauler RS, Galland GB (2001) Macromolecules 34:2411; (d) Komon ZJA, Bu X, Bazan GC (2000) J Am Chem Soc 122:1830; (e) Barnhart RW, Bazan GC (1998) J Am Chem Soc 120:1082

  9. 9.

    (a) Bianchini C, Frediani M, Giambastiani G, Kaminsky W, Meli A, Passaglia E (2005) Macromol Rapid Commun 26:1218; (b) Frediani M, Piel C, Kaminsky W, Bianchini C, Rosi L (2006) Macromol Symp 236:124; (c) Frediani M, Bianchini C, Kaminsky W (2006) Kinet Catal 47:207

  10. 10.

    McKnight AL, Waymouth RM (1998) Chem Rev 98:2587

  11. 11.

    (a) Boussie TR, Diamond GM, Goh C, Hall KA, LaPointe AM, Leclerc M, Lund C, Murphy V, Shoemaker JAW, Tracht U, Turner H, Zhang J, Uno T, Rosen RK, Stevens JC (2003) J Am Chem Soc 125:4306; (b) Eur Patent Appl EP 416 815-A2 (1991), Dow Chemical Co., invs.: Stevens JC, Timmers FJ, Wilson DR, Schmidt GF, Nickias PN, Rosen RK, Boussie TR, Diamond GM, Goh C, Hall KA, LaPointe AM, Leclerc M, Lund C, Murphy V, Shoemaker JAW, Tracht U, Turner H, Zhang J, Uno T, Knight GW, Lai S

  12. 12.

    (a) Bianchini C, Mantovani G, Meli A, Migliacci F, Laschi F (2003) Organometallics 22:2545; (b) Bianchini C, Giambastiani G, Mantovani G, Meli A, Mimeau D (2004) J Organomet Chem 689:1356; (c) Bianchini C, Gatteschi D, Giambastiani G, Guerrero Rios I, Ienco A, Laschi F, Mealli C, Meli A, Sorace L, Toti A, Vizza F (2007) Organometallics 26:726; (d) Bianchini C, Giambastiani G, Guerrero Rios I, Mantovani G, Meli A, Segarra AM (2006) Coord Chem Rev 250:1391

  13. 13.

    Kunrath FA, de Souza RF, Casagrande OL Jr, Brooks NR, Young VG Jr (2003) Organometallics 22:4739

  14. 14.

    (a) Quijada R, Dupont J, Lacerda Miranda MS, Scipioni RB, Galland GB (1995) Macromol Chem Phys 196:3991; (b) Quijada R (1996) Macromol Chem Phys 197:3091

  15. 15.

    Randall JC (1989) J Macromol Sci- Rev Macromol Chem Phys C29:201

  16. 16.

    The ethylene homopolymerization and ethylene/α-olefins co-polymerization by 2 catalysis are first order in ethylene concentration, see (a) Chakravarti S, Harmon Ray W (2001) J Appl Polym Sci 80:1096; (b) di Lena F, Quintanilla E, Chen P (2005) Chem Commun 5757; (c) Ko YS, Woo SI (2003) J Polym Sci Part A: Polym Chem 41:2171

  17. 17.

    The ethylene oligomerization by 1a–c catalysis is first order in ethylene concentration, see reference [12]

  18. 18.

    Chien JCW, Nozaki T (1993) J Polym Sci Part A: Polym Chem 31:227

  19. 19.

    (a) Philipp W, Trinkle S, Lilge D, Friedrich C, Mülhaupt R (2001) Macromol Mater Eng 286:309; (b) Philipp W, Trinkle S, Suhm J, Mäder D, Friedrich C, Mülhaupt R (2000) Macromol Chem Phys 201:604

  20. 20.

    Galland GB, Seferin M, Mauler RS, Dos Santos JHZ (1999) Polym Int 48:660

  21. 21.

    Xu G, Ruckenstein E (1998) Macromolecules 31:4724

  22. 22.

    Shiono T, Moriki Y, Ikeda T (1997) Macromol Chem Phys 198:3229

  23. 23.

    Peacock AJ (2000) Handbook of polyethylene: structures, properties, and applications. Marcel Dekker, New York

  24. 24.

    McCaffrey WC, Cooper DG, Kamal MR (1999) J Appl Polym Sci 73:1415

  25. 25.

    Li Z, Zhu N, Sun W-H, Shao C, Ke Y, Hu Y, He J (2001) Polym Int 50:1275

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Acknowledgments

Thanks are due for the financial support provided by the European Commission (NoE IDECAT, NMP3-CT-2005-011730; NANOHYBRID, NMP3-CT-2005-516972) and Ministero dell’Istruzione, dell’Università e della Ricerca of Italy (NANOPACK – FIRB project n. RBNE03R78E).

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Correspondence to Claudio Bianchini or Giuliano Giambastiani.

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Bianchini, C., Giambastiani, G., Meli, A. et al. LLDPE with Exclusively Ethyl Branches by Tandem Catalysis with Single-Site Zr(IV)/Co(II) Catalysts. Top Catal 48, 107–113 (2008). https://doi.org/10.1007/s11244-008-9053-8

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Keywords

  • Tandem catalysis
  • Cobalt
  • LLDPE
  • Zirconium