Skip to main content
SpringerLink
Log in

Effect of the acid–base properties of the support on the catalytic activity of ethylene polymerization using supported catalysts composed of Cp2ZrX2 (X = Cl, Me) and Al2O3(F)

  • Published:
Reaction Kinetics, Mechanisms and Catalysis Aims and scope Submit manuscript

Abstract

Supported catalysts Al2O3/Cp2ZrX2 and Al2O3(F)/Cp2ZrX2 (X = Me, Cl) for the ethylene polymerization were synthesized by anchoring zirconocene on alumina and alumina, modified with 1–7 wt% fluorine (Al2O3(F)). The study revealed that Al2O3(F)/Cp2ZrMe2 catalysts are active in ethylene polymerization in the absence of organoaluminum cocatalyst, whereas Al2O3(F)/Cp2ZrCl2 catalysts are active in the presence of triisobutylaluminum as a co-catalyst. The metallocene complex was strongly anchored on the support. Active component leaching was not observed during polymerization. The acid–base properties of Al2O3(F) were studied by IR spectroscopy of adsorbed probe molecules: CO, pyridine and CDCl3. A maximum activity of the catalysts was observed in the case of the Al2O3(5%F) support, containing Lewis acid sites with absorption bands (νCO) at 2210–2215 cm−1, Brønsted acid sites with a proton affinity (PA) of 1190 kJ/mol, and weak basic sites with PA 850 and 795 kJ/mol. “Cationic-like” complexes formed on the Lewis acid sites with absorption bands at 2180−2200 cm−1 are inactive at ethylene polymerization.

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

Fig. 1
Fig. 2

Similar content being viewed by others

References

  1. Hlatky GG (2000) Heterogeneous single-site catalysts for olefin polymerization. Chem Rev 100:1347–1376

    Article  CAS  Google Scholar 

  2. Chien JCW (1999) Supported metallocene polymerization catalysis. Top Catal 7:3–36

    Google Scholar 

  3. Kaminsky W (1996) New polymers by metallocene catalysis. Macromol Chem Phys 197:3907–3945

    Article  CAS  Google Scholar 

  4. Dahmen K-H, Hedden D, Burwell RL Jr, Marks TJ (1988) Organometallic molecule-support interactions. Highly active organozirconium hydrogenation catalysts and the formation of cationic species on alumina surfaces. Langmuir 4:1212–1214

    Article  CAS  Google Scholar 

  5. Finch WC, Gillespie RD, Hedden D, Marks TJ (1990) Organometallic molecule-inorganic surface coordination and catalytic chemistry. In situ CPMAS NMR delineation of organoactinide adsorbate structure, dynamics, and reactivity. JACS 112:6221–6232

    Article  CAS  Google Scholar 

  6. Ahn H, Marks TJ (1998) Supported organometallics. Highly electrophilic cationic metallocene hydrogenation and polymerization catalysts formed via protonolytic chemisorption on sulfated zirconia. JACS 120:13533–13534

    Article  CAS  Google Scholar 

  7. Nicholas CP, Ahn H, Marks TJ (2003) Synthesis, spectroscopy, and catalytic properties of cationic organozirconium adsorbates on “super acidic” sulfated alumina. “Single-site” heterogeneous catalysts with virtually 100% active sites. JACS 125:4325–4331

    Article  CAS  Google Scholar 

  8. Jezequel M, Defaud V, Ruiz-Garcia MJ, Carrillo-Hermosilla F, Neugebauer U, Niccolai GP, Lefebvre F, Bayard F, Corker J, Fiddy S, Evans J, Broyer J-P, Malinge J, Basset J-M (2001) Supported metallocene catalysts by surface organometallic chemistry. Synthesis, characterization, and reactivity in ethylene polymerization of oxide-supported mono- and biscyclopentadienyl zirconium alkyl complexes: establishment of structure/reactivity relationships. JACS 123:3520–3550

    Article  CAS  Google Scholar 

  9. Williams LA, Guo N, Motta A, Delferro M, Fragalà IL, Miller JT, Marks TJ (2013) Surface structural-chemical characterization of a single-site d0 heterogeneous arene hydrogenation catalyst having 100% active sites. PNAS 110:413–418

    Article  CAS  Google Scholar 

  10. Nicholas CP, Marks TJ (2004) Zirconium hydrocarbyl chemisorption on sulfated metal oxides: new supports, chemisorptions pathways, and implications for catalysis. Langmuir 20:9456–9462

    Article  CAS  Google Scholar 

  11. Hicks JC, Mullis BA, Jones CW (2007) Sulfonic acid functionalized SBA-15 silica as a methylaluminoxane-free cocatalyst/support for ethylene polymerization. JACS 129:8426–8427

    Article  CAS  Google Scholar 

  12. Casas E, van Grieken R, Escola JM (2012) Polymerization of ethylene with (nBuCp)2ZrCl2 supported over mesoporous SBA-15 functionalized with sulfonic acid groups. Appl Catal A 437–438:44–52

    Article  Google Scholar 

  13. Casas E, Paredes B, Van Grieken R, Escola JM (2013) (nBuCp)2ZrCl2 supported over mesoporous propyl sulfonic silica–alumina: a highly active heterogeneous catalyst for ethylene polymerization. Catal Sci Technol 3:2565–2570

    Article  CAS  Google Scholar 

  14. Yamamoto K (2009) Olefin polymerizations with zirconocene supported on SiO2 modified by MgO, NaOH and LiOH. Appl Catal A 368:65–70

    Article  CAS  Google Scholar 

  15. Campos JM, Lourenço JP, Fernandes A, Rego AM, Ribeiro MR (2009) Mesoporous Ga-MCM-41 as support for metallocene catalysts: acidity–activity relationship. J Mol Catal A 310:1–8

    Article  CAS  Google Scholar 

  16. McDaniel MP, Jensen MD, Jayaratne K, Collins KS, Benham EA, McDaniel ND, Das PK, Martin JL, Yang Q, Thorn MG, Masino AP (2008) In: Severn JR, Chadwick JC (eds) Tailor-made polymers: via immobilization of alpha-olefin polymerization catalysts. Wiley, New York, p 171

    Chapter  Google Scholar 

  17. Tabernero V, Camejo C, Terreros P, Alba MD, Cuenca T (2010) Silicoaluminates as “support activator” systems in olefin polymerization processes. Materials 3:1015–1030

    Article  CAS  Google Scholar 

  18. Motta Al, Fragalà IL, Marks TJ (2008) Links between single-site heterogeneous and homogeneous catalysis. DFT analysis of pathways for organozirconium catalyst chemisorptive activation and olefin polymerization on γ-alumina. JACS 130:16533–16546

    Article  CAS  Google Scholar 

  19. Gerberich HR, Lutinski FE, Keith Hall W (1966) Studies of the hydrogen held by solids: X. Fluorided aluminas as acid catalysts. J Catal 6:209–219

    Article  CAS  Google Scholar 

  20. Hughes TR, White HM, White RJ (1969) Brønsted and Lewis acid site concentrations in fluorided alumina from the infrared spectra of adsorbed pyridine species. J Catal 13:58–64

    Article  CAS  Google Scholar 

  21. Corma A, Fornes V, Ortega E (1985) The nature of acid sites on fluorinated γ-Al2O3. J Catal 92:284–290

    Article  CAS  Google Scholar 

  22. Paukshtis EA, Soltanov RI, Yurchenko EN, Jiratova K (1982) Acid-base properties of modified aluminas. Coll Czech Chem Commun 47:2044–2060

    Article  Google Scholar 

  23. Rodriguez LM, Alcaraz J, Hernandez M, Ben Taarit Y, Vrinat M (1998) Alkylation of benzene with propylene catalyzed by fluorined alumina. Appl Catal A 169:15–27

    Article  CAS  Google Scholar 

  24. Paukshtis EA (1992) Infrared spectroscopy of heterogeneous acid-base catalysis. Nauka, Novosibirsk (in Russian)

    Google Scholar 

  25. Paukshtis EA, Urchenko EN (1983) Study of the acid–base properties of heterogeneous catalysts by Infrared spectroscopy. Russ Chem Rev 52:242–258

    Article  Google Scholar 

Download references

Acknowledgements

This work was conducted within the framework of budget Project No. 0303-2016-0009 for Boreskov Institute of Catalysis.

Author information

Authors and Affiliations

  1. Boreskov Institute of Catalysis SB RAS, Prospekt Akad. Lavrentieva 5, Novosibirsk, Russian Federation, 630090

    V. N. Panchenko, I. G. Danilova, V. A. Zakharov, N. V. Semikolenova & E. A. Paukshtis

  2. Novosibirsk State University, Pirogova Str.2, Novosibirsk, Russian Federation, 630090

    V. N. Panchenko

  3. Tomsk State University, Prospect Lenina 36, Tomsk, Russian Federation, 634050

    E. A. Paukshtis

Authors
  1. V. N. Panchenko
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. I. G. Danilova
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. V. A. Zakharov
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. N. V. Semikolenova
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. E. A. Paukshtis
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to V. N. Panchenko.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOC 1365 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Panchenko, V.N., Danilova, I.G., Zakharov, V.A. et al. Effect of the acid–base properties of the support on the catalytic activity of ethylene polymerization using supported catalysts composed of Cp2ZrX2 (X = Cl, Me) and Al2O3(F). Reac Kinet Mech Cat 122, 275–287 (2017). https://doi.org/10.1007/s11144-017-1215-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11144-017-1215-x

Keywords

Search

Navigation