Citation: Yongxia Wang, Minghui Zuo, Yuesheng Li. Theoretical investigation of the mechanism of ethylene polymerization with salicylaldiminato vanadium(Ⅲ) complexes[J]. Chinese Journal of Catalysis, ;2015, 36(4): 657-666. doi: 10.1016/S1872-2067(14)60271-0 shu

Theoretical investigation of the mechanism of ethylene polymerization with salicylaldiminato vanadium(Ⅲ) complexes

1.
a State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, Jilin, China;

Corresponding author: Yuesheng Li,
Received Date: 7 November 2014
Available Online: 12 December 2014
Fund Project: 国家自然科学基金(21104081, 21234006). (21104081, 21234006)

The use of vanadium-based catalysts allows the preparation of high molecular mass polymers with uniform molecular mass distributions, polypropylene and ethylene/α-olefin copolymers with high α-olefin incorporation. However, the design of ligand systems with vanadium catalysts would face difficulties, because it is difficult to experimentally determine the structures of the active species of vanadium catalysts. In this paper, possible structural candidates for the active species in ethylene polymerization catalyzed by the salicylaldiminato vanadium complex combined with AlEt₂Cl were investigated using density functional theory. By comparing theoretical simulation results with previous experimental investigations, especially regarding the crucial role of the diethyaluminum chloride (AlEt₂Cl) cocatalyst, it was concluded that a neutral bimetallic species containing two Al-Cl-V bridging bonds is the most favorable structure model for the active vanadium species. A notable effect of Al co-catalysts was clarified in the theoretical investigation. During the formation of the active species, AlEt₂Cl act as an assistant for the alkylation and alkyl abstract processes of precursors. More importantly, AlEt₂Cl is necessary for the formation of the bis(chlorine-bridged) structure in the active species, which showed a notable effect on the structural stability of the active species and its catalytic activity. Additionally, we investigated the chain termination mechanism in this system.
- Quantum chemistry calculation,
- Density functional theory,
- Olefin polymerization,
- Vanadium,
- Catalytic mechanism
1. [1]
  [1] Ziegler K. Angew Chem, 1964, 76: 545
2. [2]
  [2] Natta G. Angew Chem, 1956, 68: 393
3. [3]
  [3] Carrick W L. J Am Chem Soc, 1958, 80: 6455
4. [4]
  [4] Carrick W L, Kluiber R W, Bonner E F, Wartman L H, Rugg F M, Smith J J. J Am Chem Soc, 1960, 82: 3883
5. [5]
  [5] Natta G, Pasquon I, Zambelli A. J Am Chem Soc, 1962, 84: 1488
6. [6]
  [6] Natta G, Zambelli A, Lanzi G, Pasquon I, Mognaschi E R, Segre A L, Centola P. Makromol Chem, 1965, 81: 161
7. [7]
  [7] Zambelli A, Pasquon I, Signorini R, Natta G. Makromol Chem, 1968, 112: 160
8. [8]
  [8] Doi Y, Kinoshita J, Morinaga A, Keii T. J Polym Sci A, 1975, 13: 2491
9. [9]
  [9] Christman D L, Keim G I. Macromolecules, 1968, 1: 358
10. [10]
  [10] Doi Y, Suzuki S, Soga K. Macromolecules, 1986, 19: 2896
11. [11]
  [11] Doi Y, Tokuhiro N, Nunomura M, Miyake H, Suzuki S, Soga K. In: Kaminsky W, Sinn H Eds. Transition Metals and Organometallics as Catalysts for Olefin Polymerization. Berlin: Springer-Verlag, 1988. 379
12. [12]
  [12] Adisson E, Deffieux A, Fontanille M, Bujadoux K. J Polym Sci A, 1994, 32: 1033
13. [13]
  [13] Tomov A K, Gibson V C, Zaher D, Elsegood M R J, Dale S H. Chem Commun, 2004: 1956
14. [14]
  [14] Wang W, Nomura K. Macromolecules, 2005, 38: 5905
15. [15]
  [15] Redshaw C, Rowan M A, Homden D M, Dale S H, Elsegood M R J, Matsui S, Matsuura S. Chem Commun, 2006: 3329
16. [16]
  [16] Zambelli A, Sessa I, Grisi F, Fusco R, Accomazzi P. Macromol Rapid Commun, 2001, 22: 297
17. [17]
  [17] Nomura K, Zhang S. Chem Rev, 2011, 111: 2342
18. [18]
  [18] Wu J Q, Pan L, Hu N H, Li Y S. Organometallics, 2008, 27: 3840
19. [19]
  [19] Wu J Q, Pan L, Li Y G, Liu S R, Li Y S. Organometallics, 2009, 28: 1817
20. [20]
  [20] Wu J Q, Pan L, Liu S R, He L P, Li Y S. J Polym Sci A, 2009, 47: 3573
21. [21]
  [21] Wu J Q, Mu J S, Zhang S W, Li Y S. J Polym Sci A, 2010, 48: 1122
22. [22]
  [22] Doi Y, Suzuki S, Hizai G, Soga K. In: Quirk R P Ed. Transition Metal Catalyzed Polymerization. Cambridge: Cambridge University Press, 1988. 182
23. [23]
  [23] Evens G G, Pijpers E M J, Seevens R H M. In: Quirk R P Ed. Transition Metal Catalyzed Polymerization. Cambridge: Cambridge University Press, 1988. 782
24. [24]
  [24] Coles M P, Gibson V C. Polym Bull, 1994, 33: 529
25. [25]
  [25] Niu S Q, Hall M B. Chem Rev, 2000, 100: 353
26. [26]
  [26] Lohrenz J C W, Woo T K, Fan L Y, Ziegler T. J Organomet Chem, 1995, 497: 91
27. [27]
  [27] Ziegler T. Chem Rev, 1991, 91: 651
28. [28]
  [28] Liu Z, Zhong L, Yang Y, Cheng R H, Liu B P. J Phys Chem A, 2011, 115: 8131
29. [29]
  [29] Kawamura-Kuribayashi H, Koga N, Morokuma K. J Am Chem Soc, 1992, 114: 8687
30. [30]
  [30] Kawamura-Kuribayashi H, Koga N, Morokuma K. J Am Chem Soc, 1992, 114: 2359
31. [31]
  [31] Shiga A, Kawamura H, Ebara T, Sasaki T, Kikuzono Y. J Organomet Chem, 1989, 366: 95
32. [32]
  [32] Prosenc M H, Janiak C, Brintzinger H H. Organometallics, 1992, 11: 4036
33. [33]
  [33] Wang D Q, Tomasi S, Razavi A, Ziegler T. Organometallics, 2008, 27: 2861
34. [34]
  [34] Cramer C J, Truhlar D G. Phys Chem Chem Phys, 2009, 11: 10757
35. [35]
  [35] Cavallo L, Guerra G, Vacatello M, Corradini P. Macromolecules, 1991, 24: 1784
36. [36]
  [36] Bühl M. Organometallics, 1999, 18: 4894
37. [37]
  [37] te Velde G, Bickelhaupt F M, Baerends E J, Guerra C F, Van Gisbergen S J A, Snijders J G, Ziegler T. J Comput Chem, 2001, 22: 931
38. [38]
  [38] Becke A D. Phys Rev A, 1988, 38: 3098
39. [39]
  [39] Perdew J P. Phys Rev B, 1986, 33: 8822
40. [40]
  [40] Zhao Y, Truhlar D G. J Chem Phys, 2006, 125: 194101
41. [41]
  [41] Reiher M, Salomon O, Hess B A. Theor Chem Acc, 2001, 107: 48
42. [42]
  [42] Cossee P. J Catal, 1964, 3: 80
43. [43]
  [43] Sinn H, Kaminsky W, Vollmer H J, Woldt R. Angew Chem Int Ed Engl, 1980, 19: 390
44. [44]
  [44] Kaminsky W, Miri M, Sinn H, Woldt R. Makromol Chem Rapid Commun, 1983, 4: 417
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