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Spatial Polyaluminoorganosiloxanes: Synthesis and Structural Features

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Abstract

In this work, the products of the interaction of polyvinylsilsesquioxane (PVS) and polyvinyl-polydimethylsiloxane with tris(3-chlorosulfenyl-2,4-pentanedionate) aluminum were studied. The substances were isolated through the gelation stage, and after drying, insoluble crosslinked polymers are formed. Using data from thermogravimetry (TGA), diffractometry and positron annihilation spectroscopy (PAS), the structure and composition were investigated for the first time obtained polyaluminoorganylsiloxanes. The diffractometry data demonstrated that the obtained metallochelates are spatial mesomorphic polymers with a fractal structure. Based on the calculated data of the PAS, it is shown that the annihilation of positronium in the polymer matrix occurs on oxygen, while the size of the resulting fractal turns out to be less than the molecular volume of the elementary link. The results of the thermogravimetric study indicate a greater thermal stability of aluminum compounds compared to the chromium derivatives described earlier. According to scanning electron microscopy (SEM), it was found that the surface of the formed metallochelates corresponds to the characteristic monolithic morphology of xerogels.

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No datasets were generated or analysed during the current study.

References

  1. Raygorodsky I, Kopylov V, Kovyazin A (2017) Organosiloxanes (Silicones), Polyorganosiloxane Block Copolymers: Synthesis, Properties, and Gas Permeation Membranes Based on Them. Moscow (Russia) 17–51. https://doi.org/10.1002/9781119112747.ch2

  2. Wang H, Zhang X, Li Y, Xu L-W (2022) Siloxane‐based organosilicon materials in electrochemical energy storage devices. Angew Chemie 134(49). https://doi.org/10.1002/ange.202210851

  3. Feher FJ, Newman DA, Walzer JF (1989) Silsesquioxanes as models for silica surfaces. J Am Chem Soc 111:1741–1748

    Article  CAS  Google Scholar 

  4. Levin VY, Zhdanov AA, Slonimsky GL (1982) Molecular mobility in unfilled and filled crosslinked organosilicon rubbers. High Mol Weight Compd 24(A):2115–2124 (In Russian)

    CAS  Google Scholar 

  5. Loughran GA, Griffin WR (1985) Am Chem Soc Polym Prepr 26:150–151

    CAS  Google Scholar 

  6. Leng Y, Zhao J, Jiang P, Wang J (2015) Amphiphilic porous polyhedral oligomeric silsesquioxanes (POSS) incorporated polyoxometalate-paired polymeric hybrids: Interfacial catalysts for epoxidation reactions. RSC Adv 5:17709–17715. https://doi.org/10.1039/c4ra16956e

    Article  CAS  Google Scholar 

  7. Demina NM, Trofimov AN (2020) Application of chromium (III) complexes to optimize the properties of innovative fiberglass. Bull Dagestan State Univ Series 1 Nat Sci 35:90–97 (In Russian)

    Google Scholar 

  8. Sugama T, Taylor C (1992) Pyrolysis-induced polymetallosiloxane coatings for aluminium substrates. J Mater Sci 27:1723–1734. https://doi.org/10.1007/BF01107196

    Article  CAS  Google Scholar 

  9. Muzafarov A M, Tebeneva NA, Rib EA et al (2005) Functional polymetallosiloxanes. Patent 2293746 RU, Int. Cl. C08G 79/00: 13 (In Russian)

  10. Depierro M, Pierre D, Onodera S, Rerat V (2014) Silicone Resins And Their Use in Polymers. Patent 14/358310 US, C08G 77/58; C08G 77/56; C08L 69/00; C09D 5/18; C09D 183/14: 18

  11. Tarasenkov AN, Kalinina AA, Khmelnitskaya AG et al (2020) Polysiloxane compositions and elastomeric materials with high dielectric permeability based on them. Patent 2767650 RU, Int. Cl. C08L 83/08; C08G 77/382; C08J 3/24; H01B 3/46: 16 (In Russian)

  12. Muzafarov AM, Tebeneva NA, Meshkov IB, Tarasenkov AN (2015) Functional Metallosiloxanes, Products of Their Partial Hydrolysis and Their Use. Patent 2014114570 RU, Int. Cl. C08G 79/00; C07F 7/02: 35

  13. Ashurbekova K, Ashurbekova K, Alonso-Lerma B et al (2022) Biocompatible silicon-based hybrid nanolayers for functionalization of complex surface morphologies. ACS Appl Nano Mater 5:2762–2768. https://doi.org/10.1021/acsanm.1c04428

    Article  CAS  Google Scholar 

  14. Jaber M, Miehe-Brendle J, Le Dred R (2002) Synthesis and characterization of organo phyllosilicates containing both Si, Al, and Mg. Mat Res Soc Symp Proc 726:5

    Article  Google Scholar 

  15. Jaber M, Miehé-Brendlé J, Roux M et al (2002) A new Al, Mg-organoclay. New J Chem 26:1597–1600. https://doi.org/10.1039/b206516a

    Article  CAS  Google Scholar 

  16. Jaber M, Miehé-Brendlé J, Michelin L, Delmotte L (2005) Heavy metal retention by organoclays: synthesis, applications, and retention mechanism. Chem Mater 17:5275–5281. https://doi.org/10.1021/cm050754i

    Article  CAS  Google Scholar 

  17. Timofeeva SV, Malyasova AS, Khelevina OG (2010) Protective materials of reduced fire danger. Modification of siloxane surfaces with aluminum compounds. Fire Explos Saf 19:25–29 (In Russian)

    Google Scholar 

  18. Feher FJ, Weller KJ (1990) Polyhedral aluminosilsesquioxanes as models tor aluminosilicates: unique synthesis of anionic AI/Si/O frameworks. Organometallics 9:2640–2643

    Article  Google Scholar 

  19. Shapkin NP, Svistunov GM, Shapkina VYA (1989) Synthesis and investigation of spatial polymers based on trifunctional complexes of metals and silicon compounds containing a vinyl group. High Mol Weight Compd 31(A):573–576. (In Russian)

    CAS  Google Scholar 

  20. Pervakov KA, Shapkin NP, Razov VI, Fedorets AN (2024) Composition and structure of spatial polychromoorganylsiloxanes. Silicon 12. https://doi.org/10.1007/s12633-024-02861-9

  21. Andrianov KA (1968) Methods of organoelement chemistry. Nauka, Moscow (In Russian)

    Google Scholar 

  22. Kluiber RW (1961) Inner complexes. IV. Chelate sulfenyl chlorides and thiocyanates. J Am Chem Soc 83:3030–3032. https://doi.org/10.1021/ja01475a013

    Article  CAS  Google Scholar 

  23. Razov VI, Pivtsaev AA, Trukhin VO (2018) 2D Positron annihilation time spectrometer. Fundamental and applied issues of natural science. Materials of the 61st All-Russian Scientific Conference: 179–182

  24. Svistunov GM (1989) Dissertation for the degree of PhD. Synthesis and research of ɣ-thiosubstituted β-diketonates of trivalent metals. Vladivostok (Russia): 192 (In Russian)

  25. Apanasenko OA, Vaskova ON (2008) Reactions of P-sulfenylchlorides of acetylacetonates with unsaturated compounds. Sci Works Dalrybvtuz 5(2):2762–2768 (In Russian)

    Google Scholar 

  26. Averko-Antonovich LYu (2002) Methods for studying polymer structure and properties. Kazan (Russia) (In Russian)

  27. Andrianov KA, Kononov AM, Tsvankin DYA (1968) X-ray examination of some organosilicon polymers. High Mol Weight Compds (B) X:320–323 (In Russian)

  28. Geller BE, Geller AA, Chirtulov VG (1996) Practical guide to the physicochemistry of fiber-forming polymers. Chemistry, Moscow (In Russian)

    Google Scholar 

  29. Miller RL, Boyer RF (1984) Regularities in x-ray scattering patterns from amorphous polymers. J Polym Sci Part A-2 Polym Phys 22:2043–2050. https://doi.org/10.1002/pol.1984.180221204

    Article  CAS  Google Scholar 

  30. Shapkin NP, Balanov MI, Razov VI et al (2017) Staircase polymetalsilicon nanocomplexes – polymetalphenyl siloxanes : structure and properties. J Mol Struct 25. https://doi.org/10.1016/j.molstruc.2017.11.119

  31. Alyokhina OG, Snezhko NI, Pechurova NI et al (1992) Investigation of the complexation of bivalent and trivalent metals with y-substituted acetylacetones. J Inorg Chem 37:637–641 (In Russian)

    Google Scholar 

  32. Nekrasov BV (1970) Fundamentals of general chemistry: [in 3 volumes]. Chemistry, Moscow (In Russian)

    Google Scholar 

  33. Tverdokhlebova II, Pavlova SA, Rafikov SR (1963) Izv AN SSSR. Otd. Khim. Nauk

  34. Razov V, Trukhin V (2014) Spectrum processing of positron annihilation lifetime spectroscopy based on the model of traps. Adv Mater Res 894:177–181. https://doi.org/10.4028/www.scientific.net/AMR.894.177

    Article  CAS  Google Scholar 

  35. Shapkin NP, Kulchin YuN., Razov VI et al (2011) Investigation of polyvinyl-polyphenylsiloxanes by X-ray diffractometry, positron diagnostics, NMR 29Si spectroscopy and films based on them. Proc Acad Sci Chem Ser 1614–1620 (In Russian)

  36. Shantarovich VP, Goldanskii VI (1998) Positron annihilation in free volume elements of polymer structures. Hyperfine Interact 116:67–81

    Article  CAS  Google Scholar 

  37. Shapkin NP, Razov VI, Korochentsev VV et al (2017) Study of the structure of polyphenylsiloxanes containing the metal-ions by physical–chemical methods. J Mol Struct 1145:300–308. https://doi.org/10.1016/j.molstruc.2017.05.046

    Article  CAS  Google Scholar 

  38. Sviderskii VA, Voronkov MG, Klimenko SV, Klimenko VS (2001) Thermal transformations of polymetallosiloxanes prepared by the sol-gel procedure. Russ J Appl Chem 74:1169–1172. https://doi.org/10.1023/A:1013079220534

    Article  CAS  Google Scholar 

  39. Zemskova SM, Haynes JA, Besmann TM et al (2000) Preparation and characterization of some alumosiloxanes as single-source MOCVD precursors for aluminosilicate coatings. Le J Phys IV 10:35–42. https://doi.org/10.1051/jp4:2000205

    Article  Google Scholar 

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Funding

The authors have no relevant financial or non-financial interests to disclose.

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Authors and Affiliations

  1. Far Eastern Federal University, 10 Ajax Bay, Russky Island, Vladivostok, 690922, Russia

    N. P. Shapkin, K. A. Pervakov, V. I. Razov, A. N. Fedorets & E. K. Papynov

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  2. K. A. Pervakov
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  3. V. I. Razov
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  4. A. N. Fedorets
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  5. E. K. Papynov
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Contributions

N.P. Shapkin wrote the main text of the article. K.A. Pervakov performed the synthesis of substances and conducted diffractometric and thermogravimetric studies. V.I. Razov conducted positron annihilation measurements and calculations. A.N. Fedorets conducted research on composites using a scanning electron microscope. E.K. Papynov provided text editing and consulting.

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Correspondence to K. A. Pervakov.

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Shapkin, N.P., Pervakov, K.A., Razov, V.I. et al. Spatial Polyaluminoorganosiloxanes: Synthesis and Structural Features. Silicon 16, 5161–5175 (2024). https://doi.org/10.1007/s12633-024-03068-8

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