Skip to main content
SpringerLink
Log in

Switching from Ethylene Trimerization to Ethylene Polymerization by Chromium Catalysts Bearing SNS Tridentate Ligands: Process Optimization Using Response Surface Methodology

  • Published:
Catalysis Letters Aims and scope Submit manuscript

Abstract

Two types of chromium catalysts bearing pyridine and amine based SNS ligands under the title of (pyridine-SNS-alkyl/CrCl3) and (amine-SNS-alkyl/CrCl3) were synthesized. Different thiolates such as octyl, pentyl, butyl, cyclohexyl and cyclopentyl thiolates were reacted with 2,6-pyridine-dimethylene-ditosylate (PMT)/THF solution at room temperature. Then, the purified pyridine-based SNS ligands (1–5) were reacted with CrCl3 (THF)3 to obtain the pyridine-SNS-alkyl/CrCl3 catalysts (6–10) in 50–70% yields. MMAO-activated pyridine-SNS-alkyl/CrCl3 catalysts were capable of oligomerizing ethylene. Statistical experimental design was conducted using the central composite design method and surface methodology to study of the effect of important parameters such as ethylene pressure, Al/Cr ratio, catalyst concentration and the reaction temperature on 1-C6 productivity of catalyst (7). A quadratic polynomial equation was developed to predict the 1-C6 productivity. Ethylene oligomerization using the catalyst (7) was lead to a optimized reaction conditions, including the ethylene pressure of 19.5 bar, the temperature of 58.2 °C, the MMAO co-catalyst, Al/Cr = 841 and the catalyst concentration of 8.7 µmol. The catalytic properties for ethylene oligomerization are strongly affected by reaction temperature. The experimental results indicated the reasonable agreement with the predicted values. The transformation from ethylene trimerization to ethylenev polymerization of catalyst system (7) was occurred by exchanging the reaction pressure. Influence of ligand structure with different substitutions on sulphur atom on productivity and selectivity was investigated. 1-C6 with the high selectivity and productivity 4318 (g 1-C6/g Cr h) was obtained for catalyst (7). In the second part, 1-C6 was obtained with high selectivity and productivity around 141 × 103 (g 1-C6/g Cr h) for amine-based catalyst. All amine-based catalysts (14–16) showed considerably higher catalytic activities compared to pyridine-based catalysts. According to the TGA analysis the thermal stability of pyridine-based catalysts was found to be higher than the amine-based catalysts.

Graphical Abstract

Chromium complexes bearing pyridine and amine based SNS ligands have been synthesized and their catalytic performance in ethylene oligomerization has been investigated. A switching from ethylene trimerization to ethylene polymerization of the catalyst (7) was obtained utilizing exchanging of the ethylene pressure.

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

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Scheme 2
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. Liu S, Zhang Y, Han Y et al (2017) Selective ethylene oligomerization with chromium-based metal–organic framework MIL-100 evacuated under different temperatures. Organometallics 36(3):632–638

    Article  CAS  Google Scholar 

  2. Britovsek GJ, Malinowski R, McGuinness DS et al (2015) Ethylene oligomerization beyond Schulz–Flory distributions. ACS Catal 5(11):6922–6925

    Article  CAS  Google Scholar 

  3. Rozhko E, Bavykina A, Osadchii D et al (2017) Covalent organic frameworks as supports for a molecular Ni based ethylene oligomerization catalyst for the synthesis of long chain olefins. J Catal 345:270–280

    Article  CAS  Google Scholar 

  4. Vilms AI, Babenko IA, Bezborodov VA et al (2017) Ethylene oligomerization over chromium(III) complexes with pyrrole derivatives. Petrol Chem 57(3):244–250

    Article  CAS  Google Scholar 

  5. Mohamadnia Z, Ahmadi E, Haghighi MN et al (2015) Preparation of LLDPE through tandem ethylene polymerization using chromium and zirconium catalysts. Iran Polym J 24(8):621–628

    Article  CAS  Google Scholar 

  6. Fallahi M, Ahmadi E, Ramazani A et al (2017) Trimerization of ethylene catalyzed by Cr-based catalyst immobilized on the supported ionic liquid phase. J Organomet Chem 848:149–158

    Article  CAS  Google Scholar 

  7. Xu Z, Chada JP, Xu L, et al. (2018) Ethylene dimerization and oligomerization to 1-butene and higher olefins with chromium-promoted cobalt on carbon catalyst. ACS Catal 8(3):2488–2497

    Article  CAS  Google Scholar 

  8. Lappin GR, Nemec LH, Sauer JD et al (2000) Olefins, higher. Kirk-Othmer encyclopedia of chemical technology. Wiley, New York

    Google Scholar 

  9. McGuinness DS (2010) Olefin oligomerization via metallacycles: dimerization, trimerization, tetramerization, and beyond. Chem Rev 111(3):2321–2341

    Article  Google Scholar 

  10. Bergamo AL, Da Cas HK, Rambo RS et al (2016) Chromium complexes bearing pyrazolyl-imine-phenoxy/pyrrolide ligands: synthesis, characterization, and use in ethylene oligomerization. Catal Commun 86:77–81

    Article  CAS  Google Scholar 

  11. Kuhlmann S, Paetz C, Hägele C et al (2009) Chromium catalyzed tetramerization of ethylene in a continuous tube reactor—proof of concept and kinetic aspects. J Catal 262(1):83–91

    Article  CAS  Google Scholar 

  12. Reagan WK, Freeman JW, Conroy BK et al (1994) Phillips Petroleum Company, Bartlesville

  13. Tanaka E, Urata H, Oshiki T et al (2000) Process for producing alpha-olefin oligomer compositions. EP 0611743 B2. Mitsubishi Chemical Corporation

  14. Carter A, Cohen SA, Cooley NA et al (2002) High activity ethylene trimerisation catalysts based on diphosphine ligands. Chem Commun 8:858–859

    Article  Google Scholar 

  15. Bollmann A, Blann K, Dixon JT et al (2004) Ethylene tetramerization: a new route to produce 1-octene in exceptionally high selectivities. J Am Chem Soc 126(45):14712–14713

    Article  CAS  Google Scholar 

  16. Hao Z, Xu B, Gao W (2015) Chromium complexes with N, N, N-tridentate quinolinyl anilido-imine ligand: synthesis, characterization, and catalysis in ethylene polymerization. Organometallics 34(12):2783–2790

    Article  CAS  Google Scholar 

  17. Suttil JA, Wasserscheid P, McGuinness DS et al (2014) A survey of pendant donor-functionalised (N, O) phosphine ligands for Cr-catalysed ethylene tri-and tetramerisation. Catal Sci Technol 4(8):2574–2588

    Article  CAS  Google Scholar 

  18. Alzamly A, Gambarotta S, Korobkov I (2013) Synthesis, structures, and ethylene oligomerization activity of bis (phosphanylamine) pyridine chromium/aluminate complexes. Organometallics 32(23):7107–7115

    Article  CAS  Google Scholar 

  19. Ahmadi E, Mohamadnia Z, Haghighi MN (2011) High productive ethylene trimerization catalyst based on CrCl3/SNS ligands. Catal Lett 141(8):1191

    Article  CAS  Google Scholar 

  20. Albahily K, Shaikh Y, Ahmed Z et al (2011) Isolation of a self-activating ethylene trimerization catalyst of a Cr-SNS system. Organometallics 30(15):4159–4164

    Article  CAS  Google Scholar 

  21. Mohamadnia Z, Ahmadi E, Haghighi MN et al (2011) Synthesis and optimization of ethylene trimerization using [bis-(2-dodecylsulfanyl-ethyl)-amine] CrCl3 catalyst. Catal Lett 141(3):474–480

    Article  CAS  Google Scholar 

  22. Yang Y, Liu Z, Liu B et al (2013) Selective ethylene tri-/tetramerization by in situ-formed chromium catalysts stabilized by N,P-based ancillary ligand systems. ACS Catal 3(10):2353–2361

    Article  CAS  Google Scholar 

  23. Yang Y, Gurnham J, Liu B et al (2014) Selective ethylene oligomerization with chromium complexes bearing pyridine–phosphine ligands: influence of ligand structure on catalytic behavior. Organometallics 33(20):5749–5757

    Article  CAS  Google Scholar 

  24. Zhang J, Braunstein P, Hor TA (2008) Highly selective chromium (III) ethylene trimerization catalysts with [NON] and [NSN] heteroscorpionate ligands. Organometallics 27(17):4277–4279

    Article  CAS  Google Scholar 

  25. Liu S, Pattacini R, Braunstein P (2011) Reactions between an ethylene oligomerization chromium(III) precatalyst and aluminum-based activators: alkyl and cationic complexes with a tridentate NPN ligand. Organometallics 30(13):3549–3558

    Article  CAS  Google Scholar 

  26. Simler T, Braunstein P, Danopoulos AA (2016) Chromium(II) pincer complexes with dearomatized PNP and PNC ligands: a comparative study of their catalytic ethylene oligomerization activity. Organometallics 35(24):4044–4049

    Article  CAS  Google Scholar 

  27. Jie S, Pattacini R, Rogez G et al (2009) Synthesis, structure, magnetic and catalytic properties of new dinuclear chromium(III) complexes with oxazoline alcoholate ligands. Dalton Trans 1:97–105

    Article  Google Scholar 

  28. Ai P, Danopoulos AA, Braunstein P (2015) N-Phosphanyl and N,N′-diphosphanyl-substituted N-heterocyclic carbene chromium complexes: synthesis, structures, and catalytic ethylene oligomerization. Organometallics 34(16):4109–4116

    Article  CAS  Google Scholar 

  29. Temple CN, Gambarotta S, Korobkov I et al (2007) New insight into the role of the metal oxidation state in controlling the selectivity of the Cr-(SNS) ethylene trimerization catalyst. Organometallics 26(18):4598–4603

    Article  CAS  Google Scholar 

  30. 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(18):5272–5273

    Article  CAS  Google Scholar 

  31. Komarsamy L, Bala MD, Friedrich HB et al (2011) 2,6-Bis(tosyl-oxymeth-yl)pyridine. Acta Crystallogr E 67:302

    Article  Google Scholar 

  32. Soobramoney L, Bala MD, Friedrich HB (2014) Coordination chemistry of Co complexes containing tridentate SNS ligands and their application as catalysts for the oxidation of n-octane. Dalton Trans 43(42):15968–15978

    Article  CAS  Google Scholar 

  33. Dixon JT, Green MJ, Hess FM et al (2004) Advances in selective ethylene trimerisation—a critical overview. J Organomet Chem 689(23):3641–3668

    Article  CAS  Google Scholar 

  34. Nuñez-Dallos N, Lopez-Barbosa N, Muñoz-Castro A et al (2017) A new copper (I) coordination polymer from 2, 6-bis (1H-benzotriazol-1-ylmethyl)pyridine: Synthesis, characterization, and use as additive in transparent submicron UV filters. J Coord Chem 70(19):3363–3378

    Article  Google Scholar 

  35. Janse van Rensburg W, van den Berg JA, Steynberg PJ (2007) Role of MAO in chromium-catalyzed ethylene tri-and tetramerization: a DFT study. Organometallics 26(4):1000–1013

    Article  Google Scholar 

  36. García-Muñoz RA, Morales V, Linares M et al (2014) Influence of the structural and textural properties of ordered mesoporous materials and hierarchical zeolitic supports on the controlled release of methylprednisolone hemisuccinate. J Mater Chem B 2(45):7996–8004

    Article  Google Scholar 

  37. Elowe PR, McCann C, Pringle PG et al (2006) Nitrogen-linked diphosphine ligands with ethers attached to nitrogen for chromium-catalyzed ethylene tri-and tetramerizations. Organometallics 25(22):5255–5260

    Article  CAS  Google Scholar 

  38. Yang Y, Liu Z, Zhong L et al (2011) Spin surface crossing between chromium (I)/sextet and chromium (III)/quartet without deprotonation in SNS-Cr mediated ethylene trimerization. Organometallics 30(19):5297–5302

    Article  CAS  Google Scholar 

  39. Gandon V, Agenet N, Vollhardt KP et al (2006) Cobalt-mediated cyclic and linear 2:1 cooligomerization of alkynes with alkenes: a DFT study. J Am Chem Soc 128(26):8509–8520

    Article  CAS  Google Scholar 

  40. Ghiotti G, Garrone E, Zecchina A (1991) An infrared study of CO/C2H4 coadsorption and reaction on silica-supported Cr(II) ions. J Mol Catal 65(1–2):73–83

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors would like to thank Mr. Abbas Biglari for his sincere efforts to NMR analysis of the samples.

Funding

The authors would like to thank the Iran National Science Foundation (INSF) for the financial support of this study (Grant Number 95824926) and from the Institute for Advanced Studies in Basic Sciences (IASBS) for its financial and spiritual supports.

Author information

Authors and Affiliations

  1. Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), No. 444, Prof. Yousef Sobouti Blvd., P. O. Box 45195-1159, Zanjan, 45137-66731, Iran

    Majid Soheili, Zahra Mohamadnia & Babak Karimi

Authors
  1. Majid Soheili
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Zahra Mohamadnia
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Babak Karimi
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Zahra Mohamadnia.

Ethics declarations

Conflict of interest

There is no conflict of interest for each contributing authors.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 348 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Soheili, M., Mohamadnia, Z. & Karimi, B. Switching from Ethylene Trimerization to Ethylene Polymerization by Chromium Catalysts Bearing SNS Tridentate Ligands: Process Optimization Using Response Surface Methodology. Catal Lett 148, 3685–3700 (2018). https://doi.org/10.1007/s10562-018-2571-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10562-018-2571-5

Keywords

Search

Navigation