Cover Image

Synthesis of polycalciumphenylsiloxane and composites based on the skeleton of a sea urchin with the resulting polymer

Nikolai Р. Shapkin, Irina G. Khalchenko, Kvan H. Kim, Evgeniy K. Papynov, Alexander N. Fedorets, Natalia V. Maslova, Michael I. Balanov

Abstract


In this work, we obtained polycalciumphenylsiloxane (PCPS) by the interaction of calcium bis (acetylacetonate) with polyphenylsiloxane. The first method consisted in boiling the starting reagents in toluene for several hours; the second was as follows: the mixture of the starting reagents was preliminarily treated mechanically in a ball mill, followed by boiling in toluene for several hours. Two fractions, soluble and insoluble, were isolated in both syntheses. They were investigated using IR, NMR spectroscopy, thermogravimetric analysis, and gel permeation chromatography. It was shown that the insoluble fraction is a mixture of calcium acetylacetonate and polyphenylsiloxane with a small calcium ion content. The soluble fraction is polycalciumphenylsiloxane. The yield of the soluble fraction is higher in the second synthesis method. The polymers obtained in the first and second synthesis methods are similar in composition and structure, which was confirmed by physicochemical methods. Next, the skeleton of the sea urchin Strongylocentrotus intermedius was treated with a soluble fraction in toluene. In this case, a composite was obtained, which was treated with 2–3% hydrochloric acid and then calcined at a temperature of 600 °C. At each stage, the composition of the composites was investigated using elemental analysis and IR spectroscopy. The morphology was investigated using scanning electron microscopy.

Keywords


polyphenylsiloxane; calcium acetylacetonate; sea urchin skeleton; mechanochemical activation

Full Text:

PDF

References


Coradin T, Lopes PJ. Biogenic Silica Patterning: Simple Chemistry or Subtle Biology? ChemBioChem. 2003;3:1–9. doi:10.1002/cbic.200390044

Sanchez C, Arribart H, Madeleine GG. Biomimetism and bioinspiration as tools for the design of innovative materials and systems. Nature Mater. 2005;4:277–288. doi:10.1038/nmat1339

Michalczyk MJ, Farneth WE, Vega АJ. High temperature stabilization of crosslinked siloxanes glasses. Chem Mater. 1993;5(12):1687–1689. doi:10.1021/cm00036a001

Eguchi K, Zank GA. Silicon Oxycarbide Glasses Derived from Polymer Precursors. J Sol-Gel Sci Technol. 1998;13:945–949. doi:10.1023/A:1008639727164

Choudhary R, Kumar Venkatraman S, Bulygina I, Senatov F, Kaloshkin S, Anisimova N, Kisilevskiy M, Knyazeva M, Kukui D, Walther F, Swamiappan S. Biomineralization, dissolution and cellular studies of silicate bioceramics prepared from eggshell and rice husk. Mater Sci Eng C. 2021;118:111456. doi:10.1016/j.msec.2020.111456

Levitsky MM, Zavin BG, Bilyachenko AN. Chemistry of metallasiloxanes. Current trends and new concepts. Russ Chem Rev. 2007;76(9):907–926. doi:10.1070/RC2007v076n09ABEH003691

Prockop DJ, Fertala A. The collagen fibril: the almost crystalline structure. J Struct Biol. 1998;122:111–118. doi:10.1006/jsbi.1998.3976

Erlich H, Brunner Е, Simon Р et al. Calcite reinforced silica–silica joints in the biocomposite skeleton of deep-sea glass sponges. Adv Funсt Mater. 2011;21:3473–3481. doi:10.1002/adfm.201100749

Kuzmina NP, Chechernikova MV, Martynenko LI. Calcium acetylacetonates. J Inorg Chem. 1990;35(11):2776–2780.

Shapkin NP, Kapustina AA, Dombai NV, Libanov VV, Khalchenko IG, Gardionov SV, Gribova VV. Synthesis and physicochemical characteristics of polymolybdenum(VI) phenylsiloxanes by means of different methods. Polym Bull. 2020;77(3):1177–1190. doi:10.1007/s00289-019-02790-3

Morozova NB, Zharkova GI et al. Synthesis and physical-chemical study of β-diketonates of alkaline earth metals. Novosibirsk; 1989. 28 p.

Shapkin NP, Kapustina AA, Gardionov SV, Khalchenko IG, Libanov VV, Tokar EA. Studies of Interaction of Polyphenylsiloxane with Vanadyl Bis-Acetylacetonate. Silicon. 2019;11(5):2261–2266. doi:10.1007/s12633-017-9551-z

Berman A, Addadi L, Kvick Å, Leiserowitz L, Nelson M, Weiner S. Intercalation of sea urchin proteins in calcite: study of a crystalline composite material. Sci. 1990;250:664–667. doi:10.1126/science.250.4981.664

Seto J, Ma Y, Davis S et al. Structure-property relationships of a biological mesocrystal in the adult sea urchin spine. Proc Nat Acad Sci. 2012;109:3699–3704. doi:10.1073/pnas.1109243109

Shapkin NP, Papynov EK, Panasenko AE, Khalchenko IG, Mayorov VYu, Drozdov AL, Maslova NV, Buravlev IYu. Synthesis of porous biomimetic composites: A sea urchin skeleton used as a template. Appl Sci. 2021;11;19:8897. doi:10.3390/app11198897




DOI: https://doi.org/10.15826/chimtech.2022.9.2.S6

Copyright (c) 2022 Nikolai P. Shapkin, Irina G. Khalchenko, Kvan H. Kim, Evgeniy K. Papynov, Alexander N. Fedorets, Natalia V. Maslova, Michael I. Balanov

Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 International License.

Scopus logo WorldCat logo DOAJ logo CAS logo BASE logo eLibrary logo

Chimica Techno Acta, 2014-2024
ISSN 2411-1414 (Online)
Copyright Notice