Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

High-pressure synthesis of crystalline polyethylene using optical catalysis

Nature Materials volume 3, pages 470–475 (2004)Cite this article

Abstract

Polymerization processes are probably the most relevant example of a chemical reaction activated by catalysts or radical initiators. Among polymers, polyethylene is by far the most common and largely produced. Here we present a high-pressure synthesis of high-density crystalline polyethylene by using only physical tools such as pressure and light. Low-density polyethylene is obtained by compressing ethylene at room temperature above 3 GPa in the ordered crystal phase, and a highly crystalline polymer is produced in the fluid phase at pressures lower than 1 GPa by using continuous-wave laser lines (λ ≤ 460 nm) as an optical catalyst. The photo-activation is based on a two-photon absorption process to π* antibonding states, where the change in molecular geometry favours the polymeric chain formation. The high yield and crystallinity of the polymer recovered by the photoinduced reaction and the simplicity of the synthesis make this process appealing for large-scale applications.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Evolution of the chemical reaction in the crystal phase at 3.3 GPa.
Figure 2: The effect of the irradiation wavelength on liquid ethylene at high pressure.
Figure 3: Evolution of the polymerization reaction under mUV irradiation.
Figure 4: X-ray diffraction pattern of the polymer recovered from the laser-assisted reaction in the liquid.
Figure 5: Comparison of the infrared spectra of commercial and high-pressure-synthesised polymers.
Figure 6: Comparison of the Raman spectra of commercial and high-pressure-synthesised polymers.

Similar content being viewed by others

References

  1. Hemley, R.J. Effects of high pressure on molecules. Annu. Rev. Phys. Chem. 51, 763–800 (2000).

    Article  CAS  Google Scholar 

  2. Schettino, V. & Bini, R. Molecules under extreme conditions: Chemical reactions at high pressure. Phys. Chem. Chem. Phys. 5, 1951–1965 (2003).

    Article  CAS  Google Scholar 

  3. Citroni, M., Ceppatelli, M., Bini, R. & Schettino, V. Laser-induced selectivity for dimerization versus polymerization of butadiene under pressure. Science 295, 2058–2060 (2002).

    Article  CAS  Google Scholar 

  4. Wieldraaijer, H., Schouten, J.A. & Trappeniers, N.J. Investigation of the phase diagrams of ethane, ethylene and methane at high pressures. High Temp. High Press. 15, 87–92 (1983).

    CAS  Google Scholar 

  5. Van der Putten, L., Schouten, J.A. & Trappeniers N.J. A differential scanning calorimetry study of ethylene and propane up to 10 kbar: the phase diagram of ethylene up to 23 kbar. High Temp. High Press. 18, 255–264 (1986).

    CAS  Google Scholar 

  6. Barnes, J. & Fanconi, B. Review of vibrational data and force field constants for polyethylene. J. Phys. Chem. Ref. Data 7, 1309–1322 (1978).

    Article  CAS  Google Scholar 

  7. Dorset, D.L. Applications of direct methods for structure determination to problems in electron and x-ray fibre diffraction of polymers. Rep. Progr. Phys. 66, 305–338 (2003).

    Article  CAS  Google Scholar 

  8. Nishino, T., Miyazaki, H. & Nakamae, K. X-ray diffraction of polymers under load at cryogenic temperature. Rev. Sci. Instrum. 73, 1809–1812 (2002).

    Article  CAS  Google Scholar 

  9. Qu, B.J. & Ranby, B. Photocross-linking of low density polyethylene. 2. Structure and morphology. J. Appl. Polym. Sci. 48, 711–719 (1993).

    Article  CAS  Google Scholar 

  10. Mark, J.E. Physical Properties of Polymers Handbook (AIP, New York 1996).

    Google Scholar 

  11. Hu, S.R., Kyu, T. & Stein, R.S. Characterization and properties of polyethylene blends I. Linear low-density polyethylene with high-density polyethylene. J. Polym. Sci. Polym. Phys. 25, 71–87 (1987).

    Article  CAS  Google Scholar 

  12. Wang, Z.G., Hsiao, B.S., Lopez, J. & Armistead, J.P. Crystal structure changes during isothermal crystallization, cooling and heating of linear polyethylene. J. Polym. Res. 6, 167–173 (1999).

    Article  CAS  Google Scholar 

  13. Nielsen, J.R. & Woollett, A.H. Vibrational spectra of polyethylenes and related substances. J. Chem. Phys. 26, 1391–1400 (1957).

    Article  CAS  Google Scholar 

  14. Krimm, S. Infrared spectra of high polymers. Adv. Polym. Sci. 2, 51–172 (1960).

    Article  CAS  Google Scholar 

  15. Sano, K. et al. Fourier transform Raman spectra of linear low-density polyethylene and prediction of their density by multivariate analysis. Appl. Spectrosc. 53, 551–556 (1999).

    Article  CAS  Google Scholar 

  16. Zerbi, G. & Del Zoppo, M. in Modern Polymer Spectroscopy (ed. Zerbi, G.) 87–206 (Wiley-VCH, Weinheim, 1999).

    Google Scholar 

  17. Klessinger, M. & Michl, J. Excited States and Photochemistry of Organic Molecules (VCH, New York, 1995).

    Google Scholar 

  18. Serrano-Andrès, L., Merchàn, M., Nebot-Gil, I., Lindh, R & Roos, B.O. Towards an accurate molecular-orbital theory for excited-states: ethene, butadiene, and hexatriene. J. Chem. Phys. 98, 3151–3162 (1993).

    Article  Google Scholar 

  19. Gedanken, A., Kuebler, N.A. & Robin, M.B. An MPI search for the π→3p Rydberg states of ethylene. J. Chem. Phys. 76, 46–52 (1982).

    Article  CAS  Google Scholar 

  20. Williams, B.A. & Cool T.A. Two-photon spectroscopy of rydberg states of jet-cooled C2H4 and C2D4 . J. Chem. Phys. 94, 6358–6366 (1991).

    Article  CAS  Google Scholar 

  21. Santoro, M., Ceppatelli, M., Bini, R. & Schettino, V. High-pressure photochemistry of furan crystal. J. Chem. Phys. 118, 8321–8325 (2003).

    Article  CAS  Google Scholar 

  22. Krawczyk, R.P., Viel, A., Manthe, U. & Domcke W. Photoinduced dynamics of the valence states of ethene: A six-dimensional potential-energy surface of three electronic states with several conical intersections. J. Chem. Phys. 119, 1397–1411 (2003).

    Article  CAS  Google Scholar 

  23. Sension, R.J. & Hudson, B.S. Vacuum ultraviolet resonance Raman studies of the excited electronic states of ethylene. J. Chem. Phys. 90, 1377–1389 (1989).

    Article  CAS  Google Scholar 

  24. Mestdagh, J.M., Visticot, J.P., Elhanine, M. & Soep, B. Prereactive evolution of monoalkenes excited in the 6 eV region. J. Chem. Phys. 113, 237–248 (2000).

    Article  CAS  Google Scholar 

  25. Mao, H.K., Bell, P.M., Shaner, J.V. & Steinberg, D.J. Specific volume measurements of Cu, Mo, Pd, and Ag and calibration of the ruby R1 fluorescence pressure gauge from 0.06 to 1 Mbar. J. Appl. Phys. 49, 3276–3283 (1978).

    Article  CAS  Google Scholar 

  26. Bini, R., Ballerini, R., Pratesi, G. & Jodl, H.J. Experimental setup for Fourier transform infrared spectroscopy studies in condensed matter at high pressure and low temperatures. Rev. Sci. Instrum. 68, 3154–3160 (1997).

    Article  CAS  Google Scholar 

  27. Gorelli, F., Santoro, M., Ulivi, L. & Bini, R. The ε phase of solid oxygen: evidence of an O4 molecule lattice. Phys. Rev. Lett. 83, 4093–4096 (1999).

    Article  CAS  Google Scholar 

  28. Hulbert, S.F. Models for solid-state reactions in powdered compacts: a review. J. Br. Ceram. Soc. 6, 11–20 (1969).

    CAS  Google Scholar 

Download references

Acknowledgements

We are grateful to P. R. Salvi for the useful discussions on the reaction mechanism. The authors are also grateful for the use of the HPCAT beamline at the Advanced Photon Source at the Argonne National Laboratory. Specifically we are grateful to Olga Degtyareva for her assistance in performing the diffraction analysis. This work has been supported by the European Union under contract RII3-CT-2003-506350, by the Italian Ministero dell'Università e della Ricerca Scientifica e Tecnologica (MURST) and by Consiglio Nazionale delle Ricerche.

Author information

Author notes

  1. Mario Santoro

    Present address: Geophysical Laboratory, Carnegie Institution of Washington DC, USA

Authors and Affiliations

  1. Dipartimento di Chimica dell'Università di Firenze, Via della Lastruccia 3, Sesto Fiorentino, I-50019, Firenze, Italy

    David Chelazzi, Matteo Ceppatelli, Mario Santoro, Roberto Bini & Vincenzo Schettino

  2. LENS, European Laboratory for Non-linear Spectroscopy and INFM, Via Carrara 1, Sesto Fiorentino, I-50019, Firenze, Italy

    Matteo Ceppatelli, Roberto Bini & Vincenzo Schettino

Authors
  1. David Chelazzi
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Matteo Ceppatelli
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Mario Santoro
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Roberto Bini
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Vincenzo Schettino
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Roberto Bini.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Chelazzi, D., Ceppatelli, M., Santoro, M. et al. High-pressure synthesis of crystalline polyethylene using optical catalysis. Nature Mater 3, 470–475 (2004). https://doi.org/10.1038/nmat1147

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nmat1147

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing