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Preparation and properties of methyl- and cyclohexylsilsesquioxane oligomers as organic–inorganic fillers

  • Original Paper: Sol-gel, hybrids and solution chemistries
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Abstract

The preparation of oligosilsesquioxanes from methyltrimethoxysilane and cyclohexyltrimethoxysilane for use as organic–inorganic fillers is reported. These oligomers were characterized by molecular weight, nuclear magnetic resonance analyses, and Fourier-transform infrared spectroscopy. The poly(methyl methacrylate) nanocomposites containing oligosilsesquioxanes were prepared by two methods: (i) the solution blending method and (ii) the solution–melt blending method. The solution–melt blending method was found to be a superior method for improving the thermal and mechanical properties of PMMA by intermolecular interaction between oligosilsesquioxanes fillers and PMMA.

Highlights

  • Preparation of oligosilsesquioxanes via hydrolysis–condensation reaction of alkylalkoxysilanes.

  • Characterization of oligosilsesquioxanes by nuclear magnetic resonance analyses and Fourier-transform infrared spectroscopy.

  • Difference of poly(methyl methacrylate) composites containing oligosilsesquioxanes by preparation methods.

  • PMMA composite by solution-melt-blending method showed improved properties.

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References

  1. Loy DA, Baugher BM, Baugher CR, Schneider DA, Rahimian K (2000) Substituent effects on the sol–gel chemistry of organotrialkoxysilanes. Chem Mater 12:3624–3632

    Article  CAS  Google Scholar 

  2. Baney RH, Ito M, Sakakibara A, Suzuki T (1995) Silsesquioxanes. Chem Rev 95:1409–1430

    Article  CAS  Google Scholar 

  3. Abe Y, Gunji T (2004) Oligo- and polysiloxanes. Prog Polym Sci 29:149–182

    Article  CAS  Google Scholar 

  4. Sanchez C, Philippe B, Michael P, Lionel N (2011) Applications of advanced hybrid organic–inorganic nanomaterials: from laboratory to market. Chem Soc Rev 40:696–753

    Article  CAS  Google Scholar 

  5. Zou H, Wu S, Shen J (2008) Polymer/silica nanocomposites: preparation, characterization, properties, and applications. Chem Rev 108:3893–3957

    Article  CAS  Google Scholar 

  6. Wang X, Wu L, Li J (2012) Preparation of nano poly(phenylsilsesquioxane) spheres and the influence of nano-PPSQ on the thermal stability of poly(methyl methacrylate). J Therm Anal Calorim 109:323–329

    Article  CAS  Google Scholar 

  7. Gunji T, Itagaki S, Kajiwara T, Abe Y, Hatakeyama T, Aoki R (2009) Preparation and properties of siloxane/epoxy organic-inorganic hybrid thin films, self-standing films, and bulk bodies. Polym J 41:541–546

    Article  CAS  Google Scholar 

  8. Bizet S, Galy J, Gérard JF (2006) Molecular dynamics simulation of organic–inorganic copolymers based on methacryl-POSS and methyl methacrylate. Polymer 47:8219–8227

    Article  CAS  Google Scholar 

  9. Tanaka K, Adachi S, Chujo Y (2009) Structure–property relationship of octa-substituted POSS in thermal and mechanical reinforcements of conventional polymers. J Polym Sci A 47:5690–5697

    Article  CAS  Google Scholar 

  10. Tanaka K, Yamane H, Mitamura K, Watase S, Matsukawa K, Chujo Y (2014) Transformation of sulfur to organic–inorganic hybrids employed by networks and their application for the modulation of refractive indices. J Polym Sci A 52:2588–2595

    Article  CAS  Google Scholar 

  11. Nguyen QT, Baird DG (2006) Preparation of polymer–clay nanocomposites and their properties. Adv Polym Technol 25:270–285

    Article  CAS  Google Scholar 

  12. Hayami R, Wada K, Sagawa T, Tsukada S, Watase S, Gunji T (2017)Preparation and properties of organic–inorganichybrid polymer films using [Ti4(μ3-O)(OiPr)5(μ-OiPr)3(O3PPh)3]·thf. Polym J 49:223–228

    Article  CAS  Google Scholar 

  13. Hayami R, Wada K, Nishikawa I, Sagawa T, Yamamoto K, Tsukada S, Gunji T (2017) Preparation and properties of organic–inorganic hybrid materials using titanium phosphonate clusters. Polym J 49:665–669

    Article  CAS  Google Scholar 

  14. Motaung TE, Luyt AS, Bondioli F, Messori M, Saladino ML, Spinella A, Nasillo G, Caponetti E (2012) PMMA–titania nanocomposites: properties and thermal degradation behavior. Polym Degrad Stabil 97:1325–1333

    Article  CAS  Google Scholar 

  15. Armarego WLF, Chai C (2012) Purification of laboratory chemicals, 7th ed. Butterworth-Heinemann, Oxford, UK

    Google Scholar 

  16. Takamura N, Gunji T, Hatano H, Abe Y (1999) Preparation and properties of polysilsesquioxanes: polysilsesquioxanes and flexible thin films by acid-catalyzed controlled hydrolytic polycondensation of methyl- and vinyltrimethoxysilane. J Polym Sci Part A 37:1017–1026

    Article  CAS  Google Scholar 

  17. Gunji T, Kaburagi H, Tsukada S, Abe Y (2015) Preparation, properties, and structure of polysiloxanes by acid-catalyzed controlled hydrolytic co-polycondensation of polymethyl(methoxy)siloxane and polymethoxysiloxane. J Sol-Gel Sci Technol 75:564–573

    Article  CAS  Google Scholar 

  18. Hook RJ (1996) A 29Si NMR study of the sol-gel polymerization rates of substituted ethoxysilanes. J Non-Cryst Solids 195:1–15

    Article  CAS  Google Scholar 

  19. Sugahara Y, Okada S, Kuroda K, Kato C (1992) 29Si-NMR study of hydrolysis and initial polycondensation processes of organoalkoxysilanes. I. Dimethyldiethoxysilane. J Non-Cryst Solids 139:25–34

    Article  CAS  Google Scholar 

  20. Tajima I, Yamamoto M (1987) Characterization of plasma polymers from tetramethylsilane, octamethylcyclotetrasiloxane, and methyltrimethoxysilane. J Polym Sci A 25:1737–1744

    Article  CAS  Google Scholar 

  21. Mihelčič M, Surca AK, Kreta A, Gaberšček M (2017) Spectroscopical and electrochemical characterisation of (3-mercaptopropyl)trimethoxysilane-based protective coating on aluminium alloy 2024. Croat Chem Acta 90:169–175

    Article  Google Scholar 

  22. Chen MA, Lu XB, Guo ZH, Huang R (2011) Influence of hydrolysis time on the structure and corrosion protective performance of (3-mercaptopropyl)triethoxysilane film on copper. Corros Sci 56:2793–2802

    Article  Google Scholar 

  23. Pescarmona PP, van der Waal JC, Maschmeyer T (2004) Fast, high-yielding syntheses of silsesquioxanes using acetonitrile as a reactive solvent. Eur J Inorg Chem 2004:978–983

    Article  Google Scholar 

  24. Pescarmona PP, Raimondi ME, Tetteh J, McKay B, Maschmeyer T (2003) Mechanistic study of silsesquoxane synthesis by mass spectrometry and in situ ATR FT-IR spectroscopy. J Phys Chem A 107:8885–8892

    Article  CAS  Google Scholar 

  25. Dral AP, Lievens C, ten Elshof JE (2017) Influence of monomer connectivity, network flexibility, and hydrophobicity on the hydrothermal stability of organosilicas. Langmuir 33:5527–5536

    Article  CAS  Google Scholar 

  26. Park ES, Ro HW, Nguyen CV, Jaffe RL, Yoon DY (2008) Infrared spectroscopy study of microstructures of poly(silsesquioxane)s. Chem Mater 20:1548–1554

    Article  CAS  Google Scholar 

  27. Chan CK, Peng SL, Chu IM, Ni SC (2001) Effects of heat treatment on the properties of poly(methyl methacrylate)/silica hybrid materials prepared by sol–gel process. Polymer 42:4189–4196

    Article  CAS  Google Scholar 

  28. Kashiwagi D, Inaba A, Brown JE, Hatada K, Kitayama T, Masuda E (1986) Effects of weak linkages on the thermal and oxidative degradation of poly(methyl methacrylates). Macromolecules 19:2160–2168

    Article  CAS  Google Scholar 

  29. Manring LE (1989) Thermal degradation of poly(methyl methacrylate). 2. Vinyl-terminated polymer. Macromolecules 22:2673–2677

    Article  CAS  Google Scholar 

  30. Davidson RG (1991) The effect of mechanical degradation on the pyrolysis of poly(methyl methacrylate) and its copolymers. J Anal Appl Pyrolysis 21:181–194

    Article  CAS  Google Scholar 

  31. Peterson JD, Vyazovkin S, Wight CA (1999) Stabilizing effect of oxygen on thermal degradation of poly(methyl methacrylate). Macromol Rapid Commun 20:480–483

    Article  CAS  Google Scholar 

  32. Tong Y, Lunsford H (1991) Mechanistic and kinetic studies of the reactions of gas-phase methyl radicals with metal oxides. J Am Chem Soc 113:4741–4746

    Article  CAS  Google Scholar 

  33. Tadanaga K, Azuta K, Minami T (1997) Preparation of organic–inorganic hybrid coating films from vinyltriethoxysilane–tetraethoxysilane by the sol–gel method. J Ceram Soc Jpn 105:555–558

    Article  CAS  Google Scholar 

  34. Takamura N, Okonogi H, Gunji T, Abe Y (2000) Preparation and properties of polysilsesquioxanes—preparation and properties of polymer hybrids from vinyltrimethoxysilane. Kobunshi Ronbunshu 57:198–207.

    Article  CAS  Google Scholar 

  35. Hayami R, Wada K, Miyase Y, Sagawa T, Tsukada S, Yamamoto K, Gunji T (2018) Properties and surface morphologies of organic–inorganic hybrid thin films containing titanium phosphonate clusters. Polym J 50:1169–1177

    Article  CAS  Google Scholar 

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Acknowledgements

This work was supported by JSPS KAKENHI Grant Numbers JP19K05636 and JP18K14287. Dr Kazuhiro Sayama (AIST) is greatly acknowledged for the AFM instrumentation. Prof. Yuichi Negishi and Ms Yukari Imai (Tokyo University of Sci.) are acknowledged for the assistance with MALDI-TOF-MS analysis.

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Authors and Affiliations

  1. Department of Pure and Applied Chemistry, Faculty of Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba, 278-8510, Japan

    Yohei Sato, Ryohei Hayami, Yuta Miyase, Yuzuko Ideno, Kazuki Yamamoto & Takahiro Gunji

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  1. Yohei Sato
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  2. Ryohei Hayami
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  3. Yuta Miyase
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  4. Yuzuko Ideno
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  6. Takahiro Gunji
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Correspondence to Takahiro Gunji.

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Sato, Y., Hayami, R., Miyase, Y. et al. Preparation and properties of methyl- and cyclohexylsilsesquioxane oligomers as organic–inorganic fillers. J Sol-Gel Sci Technol 95, 474–481 (2020). https://doi.org/10.1007/s10971-020-05291-2

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  • DOI: https://doi.org/10.1007/s10971-020-05291-2

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