The effect of iodo substituents in bis(phenoxyimine) zirconium complexes on the catalytic performance of homogeneous ethylene polymerization reactions

Document Type : Original research


Laboratorium für Anorganische Chemie, Universität Bayreuth, Postfach 101251, D-95440 Bayreuth, Germany


Eight different zirconium phenoxyimine complexes were synthesized, characterized and tested as catalysts for ethylene polymerization. The phenoxyimine compounds were prepared by condensation of substituted salicylaldehydes with aliphatic and aromatic amines, the substituted salicylaldehydes from ortho substituted phenols and paraformaldehyde. The introduction of iodo substituents was achieved either by iodination of the aldehyde component followed by condensation with amines or the iodination of the aldehyde after the condensation with amines or the iodination via condensation with iodo substituted amines. Deprotonation of the hydroxy function of phenoxyimine compounds and reaction with zirconium tetrachloride gave mononuclear bis(phenoxyimine) zirconium complexes in good yields. These complexes were activated with methylaluminoxane (MAO) and applied for ethylene polymerization. The performances of the various catalysts were compared and structure-property-relationships were discussed.


Main Subjects

  1. Baier MC, Zuideveld MA, Mecking S, (2014) Post-metallocenes in the industrial production of polyolefins. Angew Chem Int Ed 53: 9722-9744
  2. Yao E, Wang J, Chen Z, Ma Y (2014) Homo-and heteroligated salicylaldiminato titanium complexes with different substituents ortho to the phenoxy oxygens for ethylene and ethylene/1- hexene (Co)polymerization. Macromolecules 47:8164-8170
  3. Wang Y, Fan H, Jie S, Li B (2014) Ethylene polymerization with novel phenoxy-imine catalysts bearing 4-vinylphenyl group. China J Polym Sci 32: 854-863
  4. Xu C, Chen Z, Shen Q, Sun XL (2014) Synthesis, characterization, and catalytic behaviors of β-carbonylenamine-derived metal complexes (M= Ti, Zr) in styrene polymerization. J Organomet Chem 761: 142-146
  5. Soshnikov IE, Semikolenova NV, Ma J, Zhao K-Q, Zakharov VA, Bryliakov KP, Redshaw C, Talsi EP (2014) Selective ethylene trimerization by titanium complexes bearing phenoxy-imine ligands: NMR and EPR spectroscopic studies of the reaction intermediates. Organometallics 33: 1431-1439
  6. Redshaw C, Tang Y (2012) Tridentate ligands and beyond in group IV metal α-olefin homo-/ co-polymerization catalysis. Chem Soc Rev 41: 4484-4510
  7. Tanaka R, Viehmann P, Hecht S (2012) Bis (phenoxy-azo) titanium (IV) complexes: Synthesis, structure, and catalytic activity in styrene polymerization. Organometallics 31: 4216-4220
  8. Damavandi S, Sandaroos R, Shamekhi MA (2012) Synthesis and application of FI catalyst for ethylene polymerization. J Macromol Sci A-Pure Appl Chem 49: 339-347
  9. Krasuska A, Bialek M, Czaja K (2011) Ethylene polymerization with FI complexes having novel phenoxy-imine ligands: Effect of metal type and complex immobilization. J Polym Sci A-Polym Chem 49: 1644-1654
  10. Furuyama R, Saito J, Ishii S, Makio H, Mitani M, Tanaka H, Fujita T (2005) Fluorinated bis (phenoxy–imine) Ti complexes with MAO: Remarkable catalysts for living ethylene and syndioselective living propylene polymerization. J Organomet Chem 690: 4398-4413
  11. Bott RKJ, Hughes DL, Schormann M, Bochmann M, Lancaster SJ (2003) Monocyclopentadienyl phenoxy-imine and phenoxy-amine complexes of titanium and zirconium and their application as catalysts for 1-alkene polymerisation. J Organomet Chem 665: 135-149
  12. Mitani M, Mohri J, Yoshida Y, Saito J, Ishii S, Tsuru K, Matsui S, Furuyama R, Nakano T, Tanaka H, Kojo S, Matsugi T, Kashiwa N, Fujita T(2002) Living polymerization of ethylene catalyzed by titanium complexes having fluorine-containing phenoxy− imine chelate ligands. J Am Chem Soc 124: 3327-3336
  13. Mitani M, Furuyama R, Mohri J, Saito S, Ishii S, Terao H, Kashiwa N, Fujita T (2002) Fluorine-and trimethylsilyl-containing phenoxy− imine Ti complex for highly syndiotactic living polypropylenes with extremely high melting temperatures. J Am Chem Soc 124: 7888-7889
  14. Matsui S, Mitani M, Saito S, Trohi Y, Makio H, Matsukawa N, Takagi Y, Tsuru K, Nitabaru M, Nakano T, Tanaka H, Kashiwa N, Fujita T(2001) A family of zirconium complexes having two phenoxy− imine chelate ligands for olefin polymerization. J Am Chem Soc 123: 6847-6856
  15. Saito J, Mitani M, Mohri J, Yoshida Y, Matsui S, Ishii S, Kojoh S, Kashiwa N, Fushita T (2001) Living Polymerization of Ethylene with a Titanium Complex Containing Two Phenoxy- Imine Chelate Ligands. Angew Chem Int Ed Engl 40: 2918-2920
  16. Fujita T, Tohi Y, Mitani M, Matsui S, Saito J, Nitabaru M, Sugi K, Makio H, Tsutsui T (1998) EP 874005
  17. Matsui S, Fujita T (2001) FI catalysts: super active new ethylene polymerization catalysts. Catal Today 66: 63-73
  18. Matsui S, Mitani M, Saito J, Tohi Y, Makio H, Matsukawa N, Takagi Y, Tsuru K, Nitabaru M, Nakano T, Tanaka H, Kashiwa N, Fujita T (2001) A family of zirconium complexes having two phenoxy− imine chelate ligands for olefin polymerization. J Am Chem Soc 123: 6847-6856
  19. Matsui S, Tohi Y, Mitani M, Saito J, Makio H, Tanaka H, Nitabaru M, Nakano T, Fujita T (1999) Post-metallocenes: A new bis(salicylaldiminato) zirconium complex for ethylene polymerization. Chem Lett 28: 1263-1264
  20. Matsukawa N (2000) Olefin polymerization catalyst and process for olefin polymerization using this catalyst. EP1013674
  21. Mitani M, Yoshida Y, Mohri J, Tsuru K, Ishii S, Kojoh S, Matsugi T, Saito J, Matsukawa N, Matsui S, Nakano T, Tanaka H, Kashiwa N, Fujita T (2001) Olefin polymers and production processes thereof. WO2001055231
  22. Makio H, Kashiwa N, Fujita T (2002) FI catalysts: A new family of high performance catalysts for olefin polymerization. Adv Synth Catal 344: 477- 493
  23. Tohi Y, Nakano T, Makio H, Matsui S, Fujita T, Yamaguchi T (2004) Polyethylenes having well-defined bimodal molecular weight distributions formed with bis (phenoxy-imine) Zr complexes. Macromol Chem Phys 205: 1179-1186
  24. Görl C, Alt HG (2007) The combination of mononuclear metallocene and phenoxyimine complexes to give trinuclear catalysts for the polymerization of ethylene. J Organomet Chem 692: 5727-5753
  25. Alt HG, Schneider KJ (2008) Catalytic dimerization of propene with a bis (salicylaldiminato) nickel (II) catalyst using 2, 4, 6-trichlorophenol for isomerization reactions. Jordan J Chem 3: 11-32
  26. Görl C, Alt HG (2008) Synthesis of bis(Phenoxyimine)zirconium dichloride complexes containing bromo, iodo, or alkynyl substituted phenoxyimine ligands as catalyst precursors for the polymerization of ethylene. Jordan J Chem 3: 245-267
  27. Rimkus A (2010) Synthese von einkernigen und mehrkernigen Übergangsmetall-komplexen als katalysatoren für die ethenpolymerisation und die ethen/1-hexen-copolymerisation. Thesis, University of Bayreuth, Bayreuth
  28. Kajigaeshi S, Kakinami T, Yamasaki H, Fujisaki S, Okamoto T (1988) Bull Chem Soc Jpn 61: 600- 602
  29. Görl C (2006) Dissertation, University of Bayreuth, Bayreuth
  30. Fujita T, Tohi Y, Mitani M, Matsui S, Saito J, Nitabaru N, Sugi K, Makio H, Tsusui T (1998) Olefin polymerization catalysts, transition metal compounds, processes for olefin polymerization, and Alpha-olefin/conjugated diene copolymers. EP 0874005
  31. Makio H, Fujita T (2004) Observation and identification of the catalytically active species of bis(phenoxy-imine) group 4 transition metal complexes for olefin polymerization using 1H NMR spectroscopy. Macromol Symp 213: 221-234