Citation: Ting Fu, Rui-hua Cheng, Xue-lian He, Zhen Liu, Zhou Tian, Bo-ping Liu. Modification of the (SiO₂/MgO/MgCl₂)·TiCl_x Ziegler-Natta Polyethylene Catalysts Using the Third Metal Elements[J]. Chinese Journal of Polymer Science, ;2017, 35(6): 739-751. doi: 10.1007/s10118-017-1939-0 shu

Modification of the (SiO₂/MgO/MgCl₂)·TiCl_x Ziegler-Natta Polyethylene Catalysts Using the Third Metal Elements

State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

Corresponding author: Rui-hua Cheng, rhcheng@ecust.edu.cn Bo-ping Liu, boping@ecust.edu.cn
Received Date: 27 October 2016
Revised Date: 26 November 2016
Accepted Date: 28 November 2016

Fund Project: ajor State Basic Research Development Program of China 2012CB720502Fundamental Research Funds for the Central Universities and Research Program of Introducing Talents of Discipline of University B08021This work was financially supported by the National Natural Science Foundation of China 21674036

Various (SiO₂/MgO/MgCl₂)·TiCl_x Ziegler-Natta catalysts modified by the third metal elements were synthesized by the co-impregnation of water-soluble magnesium and the third metal salts. Several key factors including the electronegativity of the third metal elements, catalyst performances in ethylene homo-polymerization, ethylene/1-hexene copolymerization and hydrogen response were systematically investigated. Both the catalyst performance and the polymer properties are influenced by the introduction of the third metal elements. Compared with the unmodified (SiO₂/MgO/MgCl₂)·TiCl_x Ziegler-Natta catalyst, activity and 1-hexene incorporation are enhanced by the introduction of zirconium, vanadium, aluminum and chromium, while deteriorated by the addition of ferrum, nickel, molybdenum and tungsten. Correlations of the catalyst activities and 1-hexene incorporation ability with the electronegativity of the third metal elements are discovered. It is found that the lower electronegativity of the third metal elements leads to the catalyst with higher activity and higher a-olefin co-polymerization ability. The polyethylene produced by a nickel modified catalyst showed broad molecular weight distribution (MWD) and the lowest average molecular weight (MW), while by using a ferrum modified catalyst, the resulting polyethylene had the highest MW, reaching the ultra-high MW area. Vanadium and chromium modified catalysts demonstrated the best hydrogen response.
- Polyethylene,
- Ziegler-Natta polymerization,
- Copolymerization,
- Kinetics
1. [1]
  Ma, Y., Cheng, R.H., Li, J.J., Zhong, L., Liu, Z., He, X.L. and Liu, B.P., J. Organomet. Chem., 2015, 791: 311 doi: 10.1016/j.jorganchem.2015.05.058
2. [2]
  Cheng, R.H., Xue, X., Liu, W.W., Zhao, N., He, X.L., Liu, Z. and Liu, B.P., Macromol. React. Eng., 2015, 9(5): 462 doi: 10.1002/mren.v9.5
3. [3]
  Zhao, N., Cheng, R.H., He, X.L., Liu, Z. and Liu, B.P., Macromol. Chem. Phys., 2014, 215(18): 1753 doi: 10.1002/macp.v215.18
4. [4]
  Zeng, Y.N., Matta, A., Dwivedi, S., Taniike, T. and Terano, M., Macromol. React. Eng., 2013, 7(12): 668 doi: 10.1002/mren.v7.12
5. [5]
  Hsieh, J. T. , U. S. Pat. 5, 330, 950, 1994
6. [6]
  Hsieh, J. T. and Pruden, A. L. , U. S Pat. 5, 408, 015, 1995
7. [7]
  Alvarez, H. V. and Luis, J. , E. P. Pat. 1, 153, 943, 2001
8. [8]
  Cho, H.S., Chung, J.S. and Lee, W.Y., J. Mol. Catal. A: Chem., 2000, 159(2): 203 doi: 10.1016/S1381-1169(00)00222-3
9. [9]
  Cho, H.S., Choi, Y.H. and Lee, W.Y., Catal. Today, 2000, 63(2-4): 523 doi: 10.1016/S0920-5861(00)00499-5
10. [10]
  Ciaccia, E. , Vittorias, I. , Mihan, S. , Lukesova, L. , Lilge, D. , Salinas, M. H. , Meier, G. and Mannebach, G. , U. S. Pat. 0, 251, 360, 2011
11. [11]
  Bazvand, R., Bahri-Laleh, N., Nekoomanesh, M. and Abedini, H., Des. Monomers. Polym., 2015, 18(7): 599 doi: 10.1080/15685551.2015.1041089
12. [12]
  Garoff, T. and Leinonen, T., J. Mol. Catal. A: Chem., 1996, 104(3): 205 doi: 10.1016/1381-1169(95)00193-X
13. [13]
  Fregonese, D. and Bresadola, S., J. Mol. Catal. A: Chem., 1999, 145(1-2): 265 doi: 10.1016/S1381-1169(99)00015-1
14. [14]
  Phiwkliang, W., Jongsomjit, B. and Praserthdam, P., Chinese J. Polym. Sci., 2014, 32(1): 84 doi: 10.1007/s10118-014-1380-6
15. [15]
  Chen, Y.P. and Fan, Z.Q., Eur. Polym. J., 2006, 42(10): 2441 doi: 10.1016/j.eurpolymj.2006.05.015
16. [16]
  Chen, Y.P., Fan, Z.Q., Liao, J. H. and Liao, S.Q., J. Appl. Polym. Sci., 2006, 102(2): 1768 doi: 10.1002/(ISSN)1097-4628
17. [17]
  Wang, J.W., Cheng, R.H., He, X.L., Liu, Z., Tian, Z. and Liu, B.P., Macromol. Chem. Phys., 2015, 216(13): 1472 doi: 10.1002/macp.v216.13
18. [18]
  Wang, J.W., Cheng, R.H., He, X.L., Liu, Z., Zhao, N. and Liu, B.P., Macromol. React. Eng., 2016, 10(3): 246 doi: 10.1002/mren.201500056
19. [19]
  Wang, J.W., Cheng, R.H., He, X.L., Liu, Z., Zhao, N. and Liu, B.P., J. Organomet. Chem., 2015, 798(Part 2): 299
20. [20]
  Seger, M.R. and Maciel, G.E., Anal. Chem., 2004, 76(19): 5734 doi: 10.1021/ac040104i
21. [21]
  Huang, F. , Wang, J. W. , Cheng, R. H. , He, X. L. , Liu, Z. , Zhao, N. and Liu, B. P. , Macromol. React. Eng. , 2016: DOI: 10.1002/mren.201600005
22. [22]
  Fu, T., Cheng, R.H., He, X.L., Liu, Z., Tian, Z. and Liu, B.P., Polyolefins J., 2016, 3(2): 103
23. [23]
  Klabunde, U., Mulhaupt, R., Herskovitz, T., Janowicz, A.H., Calabrese, J. and Ittel, S.D., J. Polym. Sci., Part A: Polym. Chem., 1987, 25(7): 1989 doi: 10.1002/pola.1987.080250719
24. [24]
  Keim, W., Angew. Chem. Int. Ed., 1990, 29(3): 235 doi: 10.1002/(ISSN)1521-3773
25. [25]
  Ittel, S.D., Johnson, L.K. and Brookhart, M., Chem. Rev., 2000, 100(4): 1169 doi: 10.1021/cr9804644
26. [26]
  Wang, S.L., Sun, W.H. and Redshaw, C., J. Organomet. Chem., 2014, 751: 717 doi: 10.1016/j.jorganchem.2013.08.021
27. [27]
  Braca, G., Sbrana, G., Raspolli-Galletti, A.M., Altomare, A., Arribas, G., Michelotti, M. and Ciardelli, F., J. Mol. Catal. A: Chem., 1996, 107(1-3): 113 doi: 10.1016/1381-1169(95)00167-0
28. [28]
  Bailey, G. C. and Reid, J. A. , U. S. Pat. 2, 581, 228, 1952
29. [29]
  Yang, H.R., Zhang, L.T., Fu, Z.S. and Fan, Z.Q., J. Appl. Polym. Sci., 2015, 132(2): 41264
30. [30]
  Novokshonova, L. A. and Zakharov, V. A. , in "Polyolefins: 50 years after Ziegler and Natta I: polyethylene and polypropylene", ed. by Kaminsky, W. , Springer, Berlin, 2013, p. 99
31. [31]
  Hindryckx, F., Dubois, P., Jérôme, R. and Mattib, M.G., Polymer, 1998, 39(3): 621 doi: 10.1016/S0032-3861(97)00324-8
32. [32]
  Marques, M.M.V., Nunes, C.P., Tait, P.J.T. and Dias, A.R., J. Polym. Sci., Part A: Polym. Chem., 1993, 31(1): 209 doi: 10.1002/pola.1993.080310125
33. [33]
  Guastalla, G. and Giannini, U., Makromol. Chem. Rapid Commun., 1983, 4(8): 519 doi: 10.1002/marc.1983.030040803
34. [34]
  Kissin, Y.V., J. Polym. Sci., Part A: Polym. Chem., 2001, 39(10): 1681 doi: 10.1002/(ISSN)1099-0518
35. [35]
  Kissin, Y.V., Mink, R.I. and Nowlin, T.E., J. Polym. Sci., Part A: Polym. Chem., 1999, 37(23): 4255 doi: 10.1002/(ISSN)1099-0518
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Modification of the (SiO2/MgO/MgCl2)·TiClx Ziegler-Natta Polyethylene Catalysts Using the Third Metal Elements

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Modification of the (SiO₂/MgO/MgCl₂)·TiCl_x Ziegler-Natta Polyethylene Catalysts Using the Third Metal Elements