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The Effect of Al-Alkyls on the Phillips Catalyst for Ethylene Polymerization: The Case of Diethylaluminum Ethoxide (DEALE)

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Abstract

Al-alkyls are often used in the industrial practice for modifying the Phillips catalysts for polyethylene production: they are not necessary to develop the activity, but they have relevant effects on the catalysis, decreasing the induction time, promoting the in situ branching, and enhancing the H2 sensitivity for the molecular weight regulation. Herein we investigate the effect of diethylaluminum ethoxide (DEALE) on Cr(II)/SiO2 (in a stoichiometric amount of Al:Cr = 2:1), focusing the attention on the modification of the Cr(II) sites at a molecular level. Diffuse reflectance UV–Vis and FT-IR spectroscopies, applied in the presence of CO and CD3CN as molecular probes, unequivocally demonstrate that: (1) DEALE modifies only a fraction of the Cr(II) sites (ca. 30%) even if dosed in excess with respect to the Cr sites; (2) DEALE reacts with the silica surface, forming Al-grafted species which are at least partially in interaction with the Cr(II) sites and hence act as ancillary ligands; (3) the modified Cr(II) sites are more acidic and likely mono-grafted to the silica surface; the presence of Al-grafted species nearby is essential for their stabilization. Finally, kinetic experiments indicate that the modified Cr(II) sites are ca. 60 times faster in inserting ethylene than the unmodified Cr(II) sites. The intrinsic higher activity of the modified Cr(II) sites is a consequence not only of their molecular structure, but of the whole series of effects listed above.

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References

  1. Nowlin TE (2014) Business and technology of the global polyethylene industry. Wiley, New York

    Google Scholar 

  2. Market Report (2015) Global catalyst market. Acmite Market Intelligence, Ratingen

    Google Scholar 

  3. Hutley TJ, Ouederni M (2016) “Polyolefins—the history and economic impact” in polyolefin compounds and materials. Springer, Cham

    Google Scholar 

  4. Hogan JP (1958) Banks RL U.S. Patent 2,825,721

  5. McDaniel MP (2010) Adv Catal 53:123–606

    CAS  Google Scholar 

  6. Cicmil D, Meeuwissen J, Vantomme A, Wang J, van Ravenhorst IK, van der Bij HE, Munoz-Murillo A, Weckhuysen BM (2015) Angew Chem 54:13073–13079

    Article  CAS  Google Scholar 

  7. Schwerdtfeger E, Buck R, McDaniel M (2012) Appl Catal A 423–424:491

    Google Scholar 

  8. Bent BE, Nuzzo RG, Dubois LH (1989) J Am Chem Soc 111:1634

    Article  CAS  Google Scholar 

  9. Klepper KB, Nilsen O, Fjellvåg H (2010) Dalton Trans 39:11628

    Article  CAS  PubMed  Google Scholar 

  10. Kerber RN, Kermagoret A, Callens E, Florian P, Massiot D, Lesage A, Coperet C, Delbecq F, Rozanska X, Sautet P (2012) J Am Chem Soc 134:6767–6775

    Article  CAS  PubMed  Google Scholar 

  11. Li JH, DiVerdi JA, Maciel GE (2006) J Am Chem Soc 128:17093–17101

    Article  CAS  PubMed  Google Scholar 

  12. Pelletier J, Espinas J, Vu N, Norsic S, Baudouin A, Delevoye L, Trebosc J, Le Roux E, Santini C, Basset J-M, Gauvin RM, Taoufik M (2011) Chem Commun 47:2979

    Article  CAS  Google Scholar 

  13. Sauer J, Ugliengo P, Garrone E, Saunders VR (1994) Chem Rev 94:2095–2160

    Article  CAS  Google Scholar 

  14. Zhuravlev LT (2000) Colloid Surf A 173:1–38

    Article  CAS  Google Scholar 

  15. Barzan C, Bordiga S, Groppo E (2016) ACS Catal 6:2918–2922

    Article  CAS  Google Scholar 

  16. Liu BP, Terano M (2001) J Mol Catal A 172:227–240

    Article  CAS  Google Scholar 

  17. Liu B, Šindelář P, Fang Y, Hasebe K, Terano M (2005) J Mol Catal A 238:142–150

    Article  CAS  Google Scholar 

  18. Liu H, Fang Y, Nakatani H, Terano M (2004) Macromol Symp 213:37–46

    Article  CAS  Google Scholar 

  19. Xia W, Liu B, Fang Y, Hasebe K, Terano M (2006) J Mol Catal A 256:301–308

    Article  CAS  Google Scholar 

  20. Cicmil D, Meeuwissen J, Vantomme A, Weckhuysen BM (2016) ChemCatChem 8:1937–1944

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  21. Cicmil D, van Ravenhorst IK, Meeuwissen J, Vantomme A, Weckhuysen BM (2016) Catal Sci Technol 6:731–743

    Article  CAS  Google Scholar 

  22. Xia W, Tonosaki K, Taniike T, Terano M, Fujitani T, Liu BP (2009) J Appl Polym Sci 111:1869–1877

    Article  CAS  Google Scholar 

  23. Groppo E, Lamberti C, Bordiga S, Spoto G, Zecchina A (2005) Chem Rev 105:115–183

    Article  CAS  PubMed  Google Scholar 

  24. McDaniel M, Welch MB, Dreiling MJ (1983) J Catal 82:118–126

    Article  CAS  Google Scholar 

  25. Liu B, Šindelář P, Hasebe FangY, Terano K M (2005) J Mol Catal A 238:142–150

    Article  CAS  Google Scholar 

  26. Groppo E, Damin A, Otero Arean C, Zecchina A (2011) Chem Eur J 17:11110–11114

    Article  CAS  PubMed  Google Scholar 

  27. Martino GA, Barzan C, Piovano A, Budnyk A, Groppo E (2018) J Catal 357:206–212

    Article  CAS  Google Scholar 

  28. Figgis BN (1966) Introduction to ligand fields. Wiley, New York

    Google Scholar 

  29. Groppo E, Lamberti C, Bordiga S, Spoto G, Zecchina A (2005) J Phys Chem B 109:15024–15031

    Article  CAS  PubMed  Google Scholar 

  30. Ghiotti G, Garrone E, Zecchina A (1991) J Mol Catal 65:73–83

    Article  CAS  Google Scholar 

  31. Vikulov K, Spoto G, Coluccia S, Zecchina A (1992) Catal Lett 16:117–122

    Article  CAS  Google Scholar 

  32. Bade OM, Blom R, Dahl IM, Karlsson A (1998) J Catal 173:460–469

    Article  CAS  Google Scholar 

  33. Chelazzi D, Ceppatelli M, Santoro M, Bini R, Schettino V (2004) Nat Mater 3:470–475

    Article  CAS  PubMed  Google Scholar 

  34. Spoto G, Bordiga S, Garrone E, Ghiotti G, Zecchina A, Petrini G, Leofanti G (1992) J Mol Catal 74:175–184

    Article  CAS  Google Scholar 

  35. Zecchina A, Bordiga S, Spoto G, Marchese L, Petrini G, Leofanti G, Padovan M (1992) J Phys Chem 96:4991–4997

    Article  CAS  Google Scholar 

  36. Zecchina A, Garrone E, Ghiotti G, Coluccia S (1975) J Phys Chem 79:972–978

    Article  CAS  Google Scholar 

  37. Zecchina A, Groppo E (2012) Proc R Soc A 468:2087–2098

    Article  CAS  Google Scholar 

  38. Lamberti C, Zecchina A, Groppo E, Bordiga S (2010) Chem Soc Rev 39:4951–5001

    Article  CAS  PubMed  Google Scholar 

  39. Gianolio D, Groppo E, Vitillo JG, Damin A, Bordiga S, Zecchina A, Lamberti C (2010) Chem Commun 46:976–978

    Article  CAS  Google Scholar 

  40. Lupinetti AJ, Frenking G, Strauss SH (1998) Angew Chem Int Ed 37:2113–2116

    Article  CAS  Google Scholar 

  41. Lupinetti AJ, Strauss SH, Frenking G (2001) Prog Inorg Chem 49:1–112

    CAS  Google Scholar 

  42. Braterman PS (1975) Metal carbonyl spectra. Academic Press, London

    Google Scholar 

  43. Zhou MF, Andrews L, Bauschlicher CW (2001) Chem Rev 101:1931–1961

    Article  CAS  PubMed  Google Scholar 

  44. Estephane J, Groppo E, Vitillo JG, Damin A, Gianolio D, Lamberti C, Bordiga S, Quadrelli EA, Basset JM, Kervern G, Emsley L, Pintacuda G, Zecchina A (2010) J Phys Chem C 114:4451–4458

    Article  CAS  Google Scholar 

  45. Estephane J, Groppo E, Vitillo JG, Damin A, Lamberti C, Bordiga S, Zecchina A (2009) Phys Chem Chem Phys 11:2218–2227

    Article  CAS  PubMed  Google Scholar 

  46. Barzan C, Gianolio D, Groppo E, Lamberti C, Monteil V, Quadrelli EA, Bordiga S (2013) Chem Eur J 19:17277–17282

    Article  CAS  PubMed  Google Scholar 

  47. Barzan C, Groppo E, Quadrelli EA, Monteil V, Bordiga S (2012) Phys Chem Chem Phys 14:2239–2245

    Article  CAS  PubMed  Google Scholar 

  48. Morterra C, Mentruit MP, Cerrato G (2002) Phys Chem Chem Phys 4:676–687

    Article  CAS  Google Scholar 

  49. Cerruti M, Morterra C, Ugliengo P (2005) Chem Mater 17:1416–1423

    Article  CAS  Google Scholar 

  50. Morterra C, Cerrato G, Novarino E, Mentruit MP (2003) Langmuir 19:5708–5721

    Article  CAS  Google Scholar 

  51. Platero EE, Mentruit MP, Morterra C (1999) Langmuir 15:5079–5087

    Article  Google Scholar 

  52. Arean CO, Platero EE, Mentruit MP, Delgado MR, Xamena F, Garcia-Raso A, Morterra C (2000) Microporous Mesoporous Mater 34:55–60

    Article  Google Scholar 

  53. Sempels RE, Rouxhet PG (1976) J Colloid Interface Sci 55:263–273

    Article  CAS  Google Scholar 

  54. Pelmenschikov AG, Van Santen RA, Jänchen J, Meijer E (1993) J Phys Chem 97:11071–11074

    Article  CAS  Google Scholar 

  55. Chen J, Thomas JM, Sankar G (1994) J Chem Soc Faraday Trans 90:3455–3459

    Article  CAS  Google Scholar 

  56. Aboulayt A, Binet C, Lavalley J (1995) J Chem Soc Faraday Trans 91:2913–2920

    Article  CAS  Google Scholar 

  57. Cerruti M, Bolis V, Magnacca G, Morterra C (2004) Phys Chem Chem Phys 6:2468–2479

    Article  CAS  Google Scholar 

  58. Knoezinger H, Krietenbrink H (1975) J Chem Soc Faraday Trans 71:2421–2430

    Article  CAS  Google Scholar 

  59. Jeffery EA, Mole T (1968) Aust J Chem 21:2683–2686

    Article  CAS  Google Scholar 

  60. Barzan C, Piovano A, Braglia L, Martino GA, Lamberti C, Bordiga S, Groppo E (2017) J Am Chem Soc 139:17064–17073

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgements

We thank Dr. Takashi Monoi (Research & Development Division, Japan Polychem Corporation) for the stimulating discussion on the topic.

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Authors and Affiliations

  1. Department of Chemistry, NIS Centre and INSTM, University of Torino, via G. Quarello 15A, 10135, Turin, Italy

    Giorgia A. Martino, Alessandro Piovano, Caterina Barzan, Silvia Bordiga & Elena Groppo

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  1. Giorgia A. Martino
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  2. Alessandro Piovano
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  3. Caterina Barzan
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  4. Silvia Bordiga
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  5. Elena Groppo
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Corresponding author

Correspondence to Elena Groppo.

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Martino, G.A., Piovano, A., Barzan, C. et al. The Effect of Al-Alkyls on the Phillips Catalyst for Ethylene Polymerization: The Case of Diethylaluminum Ethoxide (DEALE). Top Catal 61, 1465–1473 (2018). https://doi.org/10.1007/s11244-018-1041-z

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