SpringerLink
Log in

Ethylene polymerization by a novel dinuclear heteroligated titanium complex with the ligand of (Salicylaldiminato) (β-enaminoketonato)

  • Published:
Journal of Wuhan University of Technology-Mater. Sci. Ed. Aims and scope Submit manuscript

Abstract

The condensation of acetylacetone (CH3COCH2COCH3) with benzdine (H2N-C6H4-C6H4-NH2) yielded diimine ligand 1 [HOC(Me)C(H)(Me)C=N(p-C6H4)(C6H4-p)N=C(Me)C(H)C(Me)OH)], which was converted into sodium salts. And then the sodium salts reacted with monosalicylaldiminato titanium complex 2{[3,5-di-But-2-(O)C6H2CHN(PH)]TiCl3(THF)} in dried dichloromethane to give a new benzdine-bridged binuclear complex 3{[3,5-di-But-2-(O)C6H2CHN(PH)]2[OC(Me)C(H)(Me)C=N(p-C6H4)-(C6H4-p)N=C(Me)C(H) C(Me)]Ti2Cl4}. The complex 3 was characterize by 1HNMR and elemental analysis. In the presence of MAO(methylaluminoxane), the complex 3 in toluene was effective to catalyze polymerization, affording moderately high catalytic activity 1.93×105 g PE /(mol·Ti·h)]and high molecular weight polyethylene [5.63×105 g/mol]. The high temperature gel permeation chromatography (GPC) curve of polyethylene obtained revealed a single peak, but the molecular weight distribution (MWD=3.21) is obviously broader than that of the similar mononuclear titanium complex. The melting points of the obtained polyethylene reaches 138 °C, indicating that the polyethylene is of high crystallinity.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
EUR 32.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or Ebook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price includes VAT (France)

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Small B L, Brookhart M, Bennett A M A. Highly Active Iron and Cobalt Catalysts for the Polymerization of Ethylene [J]. J. Am. Chem. Soc., 1998, 120(16):4049–4050

    Article  CAS  Google Scholar 

  2. Gibson V C, Spitzmesser S K. Advances in on-metallocene Olefin Polymerization Catalysis [J]. Chem. Rev., 2003, 103(1):283–316

    Article  PubMed  CAS  Google Scholar 

  3. Fujita T, Mitani M, Matsui S, et al. Olefin Polymerization Catalysts, Transition Metal Compounds, Processes for Olefin Polymerization, and Alpha-olefin/Conjugated Diene Coplymers[J]. Eur. Patent 0874005,1998; Chem. Abstr., 1998, 129331166.1081

    Google Scholar 

  4. Zhang D, ** G X. Novel Highly Active Bimuclear 2, 5-Disubstituted Amino-p-benzoquinone Nickel (II) Ethylene Polymerization Catalysts [J]. Organometallics, 2003, 22(14):2851–2854

    Article  CAS  Google Scholar 

  5. Liu J Y, Li Y S, Liu J Y, et al. Ethylene Polymerization with a Highly Active and Long-lifetime Macrocycle Trinuclear 2,6-Bis(imino)pyridyliron[J]. Macromolecules, 2005, 38(7):2559–2563

    Article  CAS  Google Scholar 

  6. Liu X J, Sun J Q, Zhang H Y, et al. Ethylene Polymerization by Novel Phenylene Dimethylene Bridged Homodinuclear Titanocene/MAO Systems [J]. Euro. Polym. Jnl., 2005, 41(7):1519–1524

    Article  CAS  Google Scholar 

  7. Sun J Q, Zhang H Y, Liu X J, et al. Ethylene Polymerization by Novel 4, 4-Bis(methylene) Biphenylene Bridged Homodinuclear Titanocene and Zirconocene Combined with MAO[J]. Euro. Polym. Jnl., 2006, 42(6):1259–1265

    Article  CAS  Google Scholar 

  8. Pennington D A, Harrington R W, Clegg W, et al. The Synthesis, Structure and Ethylene Polymerization Activity of Octahedral Heteroli gated(salicyladiminato) (β-enaminoketonato) Titanium Complexes: The X-ray Crystal Structure of {3-But-2-(O)C6H3CHN(PH)} {(PH) NC(Me)O}TiCl2[J]. J.Organ. Chem., 2006, 691:3183–3188

    Article  CAS  Google Scholar 

  9. Brown N M D, Nonhebe D C l. NMR Spectra of Intramolecularly Hydrogen-bonded Compounds II Schiff Bases of β-diketones and o-hydroxycarbonyl Compounds [J]. Tetrahedron, 1968, 24(16):5655–5664

    Article  CAS  Google Scholar 

  10. Nie Y J, Sun J Q, Wang L C. Ethylene Polymerization by Heteroligated (Salicylaldiminato)(β-enaminoketonato) Titanium Complex/MAO[J] J. Materials Science & Engineering, 2007, 25(4):493–496 (in Chinese)

    CAS  Google Scholar 

  11. Francis P S, Cooke R C J, J H Elliott. Fraction of Polyethylene [J]. J. Polym. Sci., 1958, 31(123):453–466

    Article  CAS  Google Scholar 

  12. Li X F, Dai K, Ye W P, Pan L, et al. New Titanium Complexes with Two β-Enaminoketonato Chelate Ligands: Syntheses, Structure, and Olefin Polymerization Activities[J]. Organometallics, 2004, (23):1223–1230

  13. Bochmann M, Lancaster S J. Base-free Cationic Zirconium Benzyl Complexes as Highly Active Polymerization Catalysts [J]. Organometallics, 1993, 12:633–640

    Article  CAS  Google Scholar 

  14. Kaminsky W, Bark A, Steiger R. Sterospecific Polymerization by Metallocene/aluminoxane Catalysts [J]. J. Mol. Catal., 1992, 74:109–119

    Article  CAS  Google Scholar 

  15. Juengling S, Muelhaupt R, Plenio H. Cooperative Effects in Binuclear Zirconocenes: Their Synthesis and Use as Catalyst in Propene Polymerization [J]. J. Organomet. Chem., 1993, 460:191–195

    Article  CAS  Google Scholar 

  16. Ushioda T, Green M L, Haggitt J, et al. Synthesis and Catalytic Properties of ansa-Binuclear Metallocenes of the Group IV Transition metals[J]. J. Organomet. Chem., 1996, 518(1–2):155–166

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemical Engineering Institute of United Chemical Reaction Engineering, College of Material and Chemical Engineering, Zhejiang University, Hangzhou, 310027, China

    Yu**g Nie, Junquan Sun, Zhengzai Cheng & Lincai Wang

Authors
  1. Yu**g Nie
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Junquan Sun
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Zhengzai Cheng
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Lincai Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Junquan Sun.

Additional information

Fund by the National Natural Science Foundation of China (20374043)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Nie, Y., Sun, J., Cheng, Z. et al. Ethylene polymerization by a novel dinuclear heteroligated titanium complex with the ligand of (Salicylaldiminato) (β-enaminoketonato). J. Wuhan Univ. Technol.-Mat. Sci. Edit. 23, 821–824 (2008). https://doi.org/10.1007/s11595-007-6821-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11595-007-6821-4

Key words

Search

Navigation