Skip to main content
Journal of Wood Science

Official Journal of the Japan Wood Research Society

Download PDF
  • Original Article
  • Published:

Newly developed nanocomposites from cellulose acetate/layered silicate/poly(ε-caprolactone): Synthesis and morphological characterization

Journal of Wood Science volume 52, pages 121–127 (2006)Cite this article

Abstract

New biodegradable cellulose acetate/layered silicate grafted poly(ε-caprolactone) [(CA/layered silicate)-g-PCL] nanocomposites were prepared by in situ polymerization of ε-caprolactone in the presence of cellulose acetate (CA) and organically modified layered silicate (OMLS). The structures of the resulting composites were investigated. X-ray diffractometry was carried out to survey general structural features of (CA/OMLS)-g-PCL nanocomposites, and revealed that OMLSs having hydroxyl groups in the organic modifiers greatly altered the layered silicate structure by monomer intercalation and successive exfoliation through its polymerization. Two of the representative cases were characterized by wide-angle and small-angle X-ray scattering analyses with a synchrotron source. The morphology of these nanocomposites was further examined by transmission electron microscopy. When SPN, one of OMLSs having one hydroxyl group in its modifier, was used, the silicate layers could not be dispersed thoroughly, but existed as aggregates consisting of several silicate layers. Among them, the crystal growth of PCL developed by transcrystallization, where the crystal growth was restricted in the confined space. When Cloisite 30B, having two hydroxyl groups within the modifier, was used, the silicate layers forming the clay were dispersed completely in the composite and random orientation of the OMLS was observed.

References

  1. Messersmith PB, Giannelis EP (1994) Synthesis and characterization of layered silicate-epoxy nanocomposites. Chem Mater 6:1719–1725

    Article  CAS  Google Scholar 

  2. Usuki A, Kawasumi M, Kojima Y, Okada A, Kurauti T, Kamigaito O (1993) Swelling behavior of montmorillonite cation exchanged for ω-amino acids by ε-caprolactam. J Mater Res 8:1174–1178

    CAS  Google Scholar 

  3. Kojima Y, Usuki A, Kawasumi M, Okada A, Kurauchi T, Kamigaito O, Kaji K (1994) Fine structure of nilon-6-clay hybrid. J Polym Sci Pol Phys 32:625–630

    CAS  Google Scholar 

  4. Messersmith PB, Giannelis EP (1995) Synthesis and barrier properties of poly(ε-caprolactone)-layered silicate nanocomposites. J Polym Sci Pol Chem 33:1047–1057

    Article  CAS  Google Scholar 

  5. Gionnelis EP (1996) Polymer layered silicate nanocomposites. Adv Mater 8:29–35

    Google Scholar 

  6. Ogata N, Jimenez G, Kawai H, Ogihara T (1997) Structure and thermal/mechanical properties of poly(l-lactide)-clay blend. J Polym Sci Pol Phys 35:389–396

    CAS  Google Scholar 

  7. Jimenez G, Ogata N, Kawai H, Ogihara T (1997) Structure and thermal/mechanical properties of poly(ε-caprolactone)-clay blend. J Appl Polym Sci 64:2211–2220

    Article  CAS  Google Scholar 

  8. LeBaron PC, Wang Z, Pinnavaia TJ (1999) Polymer-layered silicate nanocomposites: an overview. Appl Clay Sci 15:11–29

    Article  CAS  Google Scholar 

  9. Okamoto M, Nam PH, Maiti P, Kotaka T, Hasegawa N, Usuki A (2001) A house of cards structure in polypropylene/clay nanocomposites under elongational flow. Nano Lett 1:295–298

    CAS  Google Scholar 

  10. Okamoto M, Nam PH, Maiti P, Kotaka T, Nakayama T, Ohshima M, Usuki A, Hasegawa N, Okamoto N (2001) Biaxial flow-induced alignment of silicate layers in polypropylene/clay nanocomposite foam. Nano Lett 1:503–505

    CAS  Google Scholar 

  11. Lee SR, Park HM, Lim H, Kang T, Li X, Cho WJ, Ha CS (2002) Microstructure, tensile properties, and biodegradation of aliphatic polyester/clay nanocomposites. Polymer 43:2495–2500

    CAS  Google Scholar 

  12. Shen Z, Simon GP, Chen Y-B (2002) Comparison of solution intercalation and melt intercalation of polymer-clay nanocomposites. Polymer 43:4251–4260

    Article  CAS  Google Scholar 

  13. Ray SS, Okamoto K, Okamoto M (2003) Structure-property relationship in biodegradable poly(butylenes succinate)/layered silicate nanocomposites. Macromolecules 36:2355–2367

    CAS  Google Scholar 

  14. Pluta M, Galeski A, Alexandre M, Paul M-A, Dubois P (2002) Polylactide/montmorillonite nanocomposites and microcomposites prepared by melt blending: structure and some physical properties. J Appl Polym Sci 86:1497–1506

    CAS  Google Scholar 

  15. Ray SS, Yamada K, Okamoto M, Ueda K (2002) Polylactide layered silicate nanocomposite: a novel biodegradable material. Nano Lett 2:1093–1096

    CAS  Google Scholar 

  16. Yamada K, Ueda K, Ray SS, Okamoto M (2002) Preparation and properties of polylactide/layered silicate nanocomposite (in Japanese). Kobunshi Ronbunshu 59:760–766

    CAS  Google Scholar 

  17. Ray SS, Maiti P, Okamoto M, Yamada K, Ueda K (2002) New polylactide/layered silicate nanocomposites. 1. Preparation, characterization, and properties. Macromolecules 35:3104–3110

    Article  CAS  Google Scholar 

  18. Ray SS, Maiti P, Yamada K, Okamoto M, Ogami A, Ueda K (2003) New polylactide/layered silicate nanocomposites. 3. High-performance biodegradable materials. Chem Mater 15:1456–1465

    CAS  Google Scholar 

  19. Paul M-A, Alexandre M, Degee P, Henrist C, Rulmont A, Dubois P (2003) New nanocomposite materials based on plasticized poly(l-lactide) and organo-modified montmorillonites: thermal and morphological study. Polymer 44:443–450

    Article  CAS  Google Scholar 

  20. Ray SS, Yamada K, Okamoto M, Ueda K (2003) New polylactide-layered silicate nanocomposites. 2. Concurrent improvements of material properties, biodegradability and rheology. Polymer 44:857–866

    Google Scholar 

  21. Chang J-H, An YU, Cho D, Giannelis EP (2003) Poly(lactic acid) nanocomposites: comparison of their properties with mont-morrillonite and synthetic mica (II). Polymer 44:3715–3720

    CAS  Google Scholar 

  22. Ray SS, Yamada K, Okamoto M, Ueda K (2003) Control of biodegradability of polylactide via nanocomposite technology. Macromol Mater Eng 288:203–208

    Article  CAS  Google Scholar 

  23. Yoshioka M (2003) Biodegradable plastics from cellulose and lignocellulosics. In: Matsumura S, Steinbüchel A (eds) Biopolymers vol 9. Wiley, Weinheim, Germany, pp 201–235

    Google Scholar 

  24. Yoshioka M, Miyazaki T, Shiraishi N (1996) Plasticization of cellulose derivatives by reactive plasticizers I. Plasticization of cellulose acetate by kneading reaction using dibasic acid anhydrides and monoepoxides. Mokuzai Gakkaishi 42:406–416

    CAS  Google Scholar 

  25. Yoshioka M, Okajima K, Miyazaki T, Shiraishi N (2000) Plasticization of cellulose derivatives by reactive plasticizers II: characterization of plasticized cellulose acetates and their biodegradability. J Wood Sci 46:22–31

    Article  CAS  Google Scholar 

  26. Yoshioka M, Hagiwara N, Shiraishi N (1999) Thermoplasticization of cellulose acetates by grafting of cyclic esters. Cellulose 6:193–212

    Article  CAS  Google Scholar 

  27. Buchanan CM, Gardner RM, Komarck RJ (1993) Aerobic biodegradation of cellulose acetate. J Appl Polymer Sci 47:1709–1719

    CAS  Google Scholar 

  28. Bittiger B, Marchessault RH (1970) Crystal structure of poly-ε-caprolactone. Acta Crystallogr B 26:1923–1927

    Article  CAS  Google Scholar 

  29. Takahashi T, Nishio Y, Mizuno H (1987) Crystallization behavior of polybutene-1 in the anisotropic system blended with polypropylene. J Appl Polym Sci 34:2757–2768

    Article  CAS  Google Scholar 

  30. Li Y, Kaito A (2003) Crystallization and orientation behaviors of poly(vinylidene fluoride) in the oriented blend with nylon 11. Polymer 44:8167–8176

    CAS  Google Scholar 

  31. Chujo K (2002) On the Relation between the degree of delamination and the mechanical properties of polymer/clay nanocomposites (in Japanese). Seikei-Kakou 14:686–687

    CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Division of Forest and Biomaterials Science, Graduate School of Agriculture, Kyoto University, Kitashirakawa Oiwake-cho, Sakyo-ku, Kyoto, 606-8502, Japan

    Mariko Yoshioka, Keiji Takabe & Yoshiyuki Nishio

  2. Research Institute for Sustainable Humanosphere, Kyoto University, Uji, 611-0011, Japan

    Junji Sugiyama

Authors
  1. Mariko Yoshioka
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Keiji Takabe
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Junji Sugiyama
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yoshiyuki Nishio
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Mariko Yoshioka.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Yoshioka, M., Takabe, K., Sugiyama, J. et al. Newly developed nanocomposites from cellulose acetate/layered silicate/poly(ε-caprolactone): Synthesis and morphological characterization. J Wood Sci 52, 121–127 (2006). https://doi.org/10.1007/s10086-005-0742-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10086-005-0742-7

Key words