View More View Less
  • 1 Daqing Petrochemical Research Center, PetroChina Company Limited, Daqing 163714, Heilongjiang, China
  • 2 School of Material Science and Engineering, Qiqihar University, Qiqihar 161006, Heilongjiang, China
  • 3 Department of Chemical Engineering, Harbin University of Technology, Harbin 150001, Heilongjiang, China
Restricted access

Abstract

In this article, (Ph2P)2N(cyclopentyl) ligands were prepared. The catalyst system that consists of main catalyst acetylacetone chromium (Cr(acac)3), cocatalyst triethyaluminium (TEA), ligands composited with 2,5-dimmethylpyrrole (DMP) and (Ph2P)2N(cyclopentyl) was used to trimerize ethylene to 1-hexene. The catalytic activity and selectivity of ethylene trimerization were studied under various reaction conditions (reaction temperature, ethylene pressure and cocatalysts). It was found that the Cr(acac)3/TEA/(Ph2P)2N(cyclopentyl) · (DMP) catalytic system catalyzed ethylene trimerization in situ, which gave an activity of 273.83 kg/gCr h−1, selectivity of 95.74%, and a spot of PE at 50 °C and 5 MPa ethylene pressure. TEA was an effective cocatalyst for ethylene trimerization. Compared with a single ligand such as (Ph2P)2N(cyclopentyl) or DMP, the composite ligands combined their respective advantages.

  • 1. Manyik, RM, Walker, WE, Wilson, TP 1977 A soluble chromium-based catalyst for ethylene trimerization and polymerization. J Catal 47:197209 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 2. Briggs JR (1987) Process for trimerization. US, 4668838. Union Carbide Corporation, Danbury.

  • 3. Wu FJ (1992) Ethylene oligomerization: EP, 0537609. Albemarle Corporation, St Baton Rouge.

  • 4. Yoshida T , Yamamoto T, Okada H, et al (2002) Catalyst for trimerization of ethylene and process for trimerizing ethylene using the catalyst. US, 0035029. Tosoh Corporation, Tokyo.

    • Search Google Scholar
    • Export Citation
  • 5. Ittle, SD, Johnson, LK, Brookhart, M 2000 Late-metal catalysts for ethylene homo- and copolymerization. Chem Rev 100:11691203 .

  • 6. Aoshima T , Urata T (1999) Method for production of alpha-olefin low grade polymers-comprises conducting low grade polymerization in the presence of a catalyst prepared from a chromium compound in which three hydroxyl groups are bonded to the metal: JP, 11222445. Mitsubishi Chemical Corporation, Chiyoda-ku.

    • Search Google Scholar
    • Export Citation
  • 7. Wu FJ . (1995) Ethylene trimerization: US, 5811618. Amoco Corporation, Chicago.

  • 8. Wass DF (2002) Olefin trimerisation using a catalyst comprising a source of chromium, molybdenum or tungsten and a ligand containing at least one phosphorous, arsenic or antimony atom bound to at least one (hetero)hydrocarbyl group: WO, 02/004119. BP Chemicals Ltd, Saltend.

    • Search Google Scholar
    • Export Citation
  • 9. Carter, A, Cohen, SA, Cooley, NA et al. 2002 High activity ethylene trimerisation catalysts based on diphosphine ligands. Chem Commun 8:858859 .

  • 10. McGuinness, DS, Wasserscheid, P, Keim, W et al. 2003 First Cr(III)-SNS complexes and their use as highly efficient catalysts for the trimerization of ethylene to 1-hexene. J Am Chem Soc 125:52725273 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 11. Dixon JT , Wasserscheid P, McGuinness DS et al. (2003) Trimerisation and oligomerisation of olefins using a chromium based catalyst. WO, 053890. Sasol Technology (Ptv)Ltd, Johannesburg.

    • Search Google Scholar
    • Export Citation
  • 12. McGuinness, DS, Rucklidge, AJ, Tooze, RP et al. 2007 Cocatalyst influence in selective oligomerization: effect on activity, catalyst stability, and 1-hexene/1-octene selectivity in the ethylene trimerization and tetramerization reaction. Organometallics 26:25612569 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 13. McGuinness, DS, Overett, M, Tooze, RP et al. 2007 Ethylene tri- and tetra-merization with borate cocatalyst: effects on activity, selectivity, and catalyst degradation pathways. Organometallics 26:11081111 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 14. Blann, K, Bollmann, A, Bod, H et al. 2007 Ethylene tetramerisation:subtle effects exhibited by N-substituted diphosphinoamine ligands. J Catal A Chemical 249:244249.

    • Search Google Scholar
    • Export Citation
  • 15. McGuinness, DS 2011 Olefin oligomerization via metallacycles: dimerization, trimerization, tetramerzation, and beyond. Chem Rev 111:23212341 .

  • 16. Killian, E, Blann, K, Bollmann, A et al. 2007 The use of bis(diphenylphosphino)amines with N-aryl functionalities in selective ethylene tri- and tetramerisation [J]. J Mole Catal A Chemical 270:214218 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 17. McGuinness, DS, Wasserscheid, P, Keim, W et al. 2003 Novel Cr-PNP complexes as catalysts for the trimerisation of ethylene. Chem Commun 3:334335 .

  • 18. McGuinness, DS, Brown, DB, Tooze, RP et al. 2006 Ethylene trimerization with Cr-PNP and Cr-SNS complexes: effect of ligand structure, metal oxidation state, and role of activator on catalysis. Organometallics 25:36053610 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 19. Zhang, BJ, Wang, YJ, Jiang, T, Xing, LH 2006 Synthesis of diphenylphosphinoamine ligands and their catalytic performance for ethylene tetramerization with Cr(III) Compounds. Chin J Catal 27:416420.

    • Search Google Scholar
    • Export Citation
  • 20. Zhang, BJ, Wang, G, Wang, SH, Zhang, DS, Wang, YJ 2007 Cr(III)-based catalyst system for oligomerization of ethylene to 1-octene with high selectivity. Chin J Catal 28:317320.

    • Search Google Scholar
    • Export Citation