Skip to main content
SpringerLink
Log in

Synthesis and physicochemical characteristics of polymolybdenum(VI) phenylsiloxanes by means of different methods

  • Original Paper
  • Published:
Polymer Bulletin Aims and scope Submit manuscript

Abstract

Interaction of molybdenyl(VI) bis(acetylacetonate) with polyphenylsiloxane in xylene and under mechanochemical activation conditions has been investigated. The interaction in solution proceeds with splitting of the siloxane bond and formation of polymolybdenum(VI) phenylsiloxane with different silicon/metal ratios. The fractions with the silicon/metal ratio < 2 are characterized with high degree of crystallinity and low solubility, whereas those with the ratio > 2 are amorphous. The interaction of the above reagents under mechanical activation conditions proceeds with the formation of soluble polymers similar to those obtained in a solution with the silicon/molybdenum ratio equal to 2.6. The crystal chemistry parameters of the fraction obtained in solution with the ratio Si/Mo equals to 1:2 have been calculated on the basis of the X-ray diffraction analysis data using the Debye–Shearer equation. It has been demonstrated that the chain cross section found using the Miller–Boyer method coincides with that calculated geometrically on the basis of literature data on bond lengths and angles. It is shown that the interaction of molybdenyl(VI) bis(acetylacetonate) with polyphenylsiloxane takes place in solution more deeply than under the conditions of mechanochemical activation and is accompanied by the process of separation siloxanes connection. This leads to the formation of a fraction with smaller ratio of substances than the initial ratio.

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
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Baňares MA, Hu H, Wachs IE (1994) Molybdena on silica catalysts: role of preparation methods on the structure-selectivity properties for the oxidation of methanol. J Catal 150:407–420. https://doi.org/10.1006/jcat.1994.1359

    Article  Google Scholar 

  2. Wada K, Yoshida K, Watanabe Y (1995) Selective photooxidation of light alkanes to oxygenates using supported molybdenum oxide catalysts. J Chem Soc Faraday Trans 91:1647–1649. https://doi.org/10.1039/FT9959101647

    Article  CAS  Google Scholar 

  3. Van Der Voort Pascal, Mitchell Mark B, Vansant Etienne F, White Mark G (1997) The uses of polynuclear metal complexes to develop designed dispersions of supported metal oxides: part I. Synthesis and characterization. Interface Sci 5:169–197. https://doi.org/10.1023/A:1008669528505

    Article  Google Scholar 

  4. Van der Voort P, Van Wekzenis R, de Ridder M, Brongersma HH, Baltes M, Mathieu M, Vande Ven PC, Vansant EF (2002) Controlled deposition of iron oxide on the surface of zirconia by the molecular designed dispersion of Fe(acac)3. A spectroscopic study. Langmuir 18:4420–4425. https://doi.org/10.1021/la025679u

    Article  CAS  Google Scholar 

  5. Kenvin JC, White MG, Mitchell MB (1991) Preparation and characterization of supported mononuclear metal complexes as model catalysts. Langmuir 7:1198–1204. https://doi.org/10.1021/la00054a030

    Article  CAS  Google Scholar 

  6. Feher FJ, Blanski RL (1990) Polyhedral oligometallasilasesquioxanes as models for silica-supported catalysts: chromium attached to two vicinal siloxy groups. J Chem Soc Chem Commun. https://doi.org/10.1039/C39900001614

    Article  Google Scholar 

  7. Collart O, Van Der Voort P, Vansant EF, Gustin E, Bouwen A, Schoemaker D, Ramachandra Rao R, Weckhuysen BM, Schoonheydt RA (1999) Spectroscopic characterization of an MoOx layer on the surface of silica. An evaluation of the molecular designed dispersion method. Phys Chem 1:4099–4104. https://doi.org/10.1039/a903110c

    Article  CAS  Google Scholar 

  8. Papynov EK, Shapkin NP (2009) Solid waste disposal using thermal cracking. Russ J Chem Technol 10:48–52 (ISSN 0579-2991)

    Google Scholar 

  9. Shapkin NP, Zolotar’ GYa, Shapkina VYa (1983) Investigation of the interaction of phenylhydroxysilanes with iron three acetylacetonate. Deposited ONIITEKChem. 420-XII D 83

  10. Shapkin NP, Zolotar’ GYa, Shapkina VYa, Bessonova VI, Alikovsky AV (1985) Interaction of gallium acetylacetonates, nickel, copper with diphenylsilanediol. Deposited ONIITEKChem. 753 XII-85 D

  11. Kapustina AA, Shapkin NP, Makedonskaya ES (2010) Synthesis of ferrodiphenylsiloxanes by the method of mechanochemical activation. Butler Bull 19:7–11 (ISSN: 2074-0212)

    Google Scholar 

  12. Leont’ev LB, Shapkin NP, Leont’ev AL, Makarov VN (2016) RF Patent 2580270. Bull. 3

  13. Tutov MV, Shapkin NP, Kondrikov NB, Kuryavyi VG (2015) Formation of nanostructured light guiding films based on octavinylsilsesquioxane and polyvinylsilsesquioxane using structured aluminum oxide. Russ J Nanotechnol 10:90–94

    Google Scholar 

  14. Andrianov KA, Khananashvili LM (1973) Technology of organometallic monomers and polymers. Chemistry, Moscow

    Google Scholar 

  15. Shapkin NP, Kul’chin YuN, Razov VI, Voznesenskii SS, Bazhenov VV, Tutov MV, Stavnistyi NN, Kuryavyi VG, Slobodyuk AB (2011) The study of polyvinylpolyphenylsilsesquioxanes using X-ray diffractometry, positron diagnostics, Si29 NMR spectroscopy and the study of films based on them. Russ Chem Bull 60:1640–1646. https://doi.org/10.1007/s11172-011-0245-1

    Article  CAS  Google Scholar 

  16. Krasochka ON, Sokolova YuA, Atovnyan LO (1975) Crystal and molecular structures of molybdenum bis-acetylacetonate, MoO2(C5H7O2)2. J Struct Chem 16:648–650

    Article  Google Scholar 

  17. Miller RL, Boyer RF (1984) Regularities in X-ray scattering patterns from amorphous polymers. J Polymer Sci 22:2043–2050. https://doi.org/10.1002/pol.1984.180221204

    Article  CAS  Google Scholar 

  18. Shapkin NP, Leont’ev LB, Makarov VN, Khal’chenko IG, Korochentsev VV, Shkuratov AL (2014) Vermiculite-based organosilicate antifriction composites as coatings on friction surfaces of steel articles. Russ J Appl Chem 87:1810–1816. https://doi.org/10.1134/s1070427214120039

    Article  CAS  Google Scholar 

  19. Brown JF, Vogt LH, Prescott PJ (1964) Preparation and characterization of the lower equilibrated phenylsilsesquioxanes. J Am Chem Soc 86:1120–1125

    Article  CAS  Google Scholar 

  20. Jones MM (1959) A new method of preparing some acetylacetonate complexes. J Am Chem Soc 81:3188–3189. https://doi.org/10.1021/ja01522a005

    Article  CAS  Google Scholar 

  21. Shapkin NP, Balanov MI, Razov VI, Gardionov SV, Mayorov VY, Tokar EA, Papynov EK, Korochentsev VV, Leont’ev LB, Slobodyuk AB, Modin EB (2018) Staircase polymetalsilicon nanocomplexes: polymetalphenyl siloxanes—structure and properties. J Mol Struct 1156:424–432. https://doi.org/10.1016/j.molstruc.2017.11.119

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The rest of the work was financially supported by a grant from the Ministry of Education and Science of the Russian Federation (Project No. 4.8063.2017/8.9).

Author information

Authors and Affiliations

  1. Far Eastern Federal University, 8, Sukhanova Str., Vladivostok, Russia, 690950

    N. P. Shapkin, A. A. Kapustina, N. V. Dombai, V. V. Libanov, I. G. Khalchenko, S. V. Gardionov & V. V. Gribova

Authors
  1. N. P. Shapkin
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. A. A. Kapustina
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. N. V. Dombai
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. V. V. Libanov
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. I. G. Khalchenko
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. S. V. Gardionov
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. V. V. Gribova
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to N. P. Shapkin.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Shapkin, N.P., Kapustina, A.A., Dombai, N.V. et al. Synthesis and physicochemical characteristics of polymolybdenum(VI) phenylsiloxanes by means of different methods. Polym. Bull. 77, 1177–1190 (2020). https://doi.org/10.1007/s00289-019-02790-3

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00289-019-02790-3

Keywords

Search

Navigation