Skip to main content
SpringerLink
Log in

Constrained polymer chain behavior observed in their non-stoichiometric cyclodextrin inclusion complexes

  • Original Article
  • Published:
Journal of Inclusion Phenomena and Macrocyclic Chemistry Aims and scope Submit manuscript

Abstract

Much has been learned from inclusion compounds (IC’s) formed between guest polymers and host cyclodextrins (CDs) [polymer-CD-ICs] by examining the properties of the fully covered guest polymers, as well as those coalesced neat bulk samples of guest polymers obtained upon removal of the host CDs. However, what can be gained from studying the properties of the restrained unthreaded portions of polymer chains that “dangle” from non-stoichiometric (n-s)-polymer-CD-IC’s? We attempt to assist in answering this question by observing (n-s)-polymer-CD-IC’s formed between amorphous atactic-poly(methyl methacrylate) (PMMA) and γ-CD, as well as the IC formed between a synthesized poly(ε-caprolactone)-poly(propylene glycol)-poly(ε-caprolactone) (PCL-PPG-PCL) triblock copolymer and β-CD, which was presumed to have threaded and unthreaded PPG and PCL blocks. Though our (n-s)-PMMA-γ-CD-IC samples were found to exhibit extremely heterogeneous behaviors, glass transition temperature increases of up to 27 °C above that of neat PMMA were observed. X-ray diffraction data indicates modest γ-CD crystallinity at partial coverages of PMMA, with a crystal structure similar to that of the IC with full coverage. On the other hand, XRD, DSC and FTIR data revealed an almost total disruption of PCL block crystallinity upon complexation of PCL-PPG-PCL with β-CD, suggesting either partial threading and coverage of the PCL blocks by β-CD or their partial mixing with the PPG blocks covered with β-CD.

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
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  1. Tonelli, A.E.: Molecular processing of polymers with cyclodextrins. Adv. Polym. Sci. 222, 115–173 (2009)

    CAS  Google Scholar 

  2. Dong, T., Mori, T., Pan, P., Kai, W., Zhu, B., Inoue, Y.J.: Crystallization behavior and mechanical properties of poly(ε-caprolactone)/cyclodextrin biodegradable composites. Appl. Polym. Sci. 112, 2351–2357 (2009)

    Article  CAS  Google Scholar 

  3. Dong, T., He, Y., Zhu, B., Shin, K., Inoue, Y.: Nucleation mechanism of α-cyclodextrin-enhanced crystallization of some semicrystalline aliphatic polymers. Macromolecules 38, 7736–7744 (2005)

    Article  CAS  Google Scholar 

  4. Dong, T., Kai, W., Pan, P., Cao, A., Inoue, Y.: Effects of host−guest stoichiometry of α-cyclodextrin−aliphatic polyester inclusion complexes and molecular weight of guest polymer on the crystallization behavior of aliphatic polyesters. Macromolecules 40, 7244–7251 (2007)

    Article  CAS  Google Scholar 

  5. Mohan, A., Joyner, X., Kotek, R., Tonelli, A.E.: Constrained/directed crystallization of Nylon-6. I. Nonstoichiometric inclusion compounds formed with cyclodextrins. Macromolecules 42, 8983–8991 (2009)

    Article  CAS  Google Scholar 

  6. Luo, H., Liu, Y., Yu, Z., Zhang, S., Li, B.: Novel Biodegradable shape memory material based on partial inclusion complex formation between α-cyclodextrin and poly(ε-caprolactone). Biomacromolecules 9, 2573–2577 (2008)

    Article  CAS  Google Scholar 

  7. Luo, H., Fan, M., Yu, Z., Meng, X., Li, B., Zhang, S.: Preparation and properties of degradable shape memory material based on partial α-cyclodextrin–poly(ε-caprolactone) inclusion complex. Macromol. Chem. Phys. 210, 669–676 (2009)

    Article  CAS  Google Scholar 

  8. Harada, A., Okada, M., Li, J., Kamachi, M.: Preparation and characterization of inclusion complexes of poly(propylene glycol) with cyclodextrins. Macromolecules 28, 8406–8411 (1995)

    Article  CAS  Google Scholar 

  9. Shuai, X., Porbeni, F., Wei, M., Bullions, T., Tonelli, A.: Inclusion complex formation between α, γ-cyclodextrins and a triblock copolymer and the cyclodextrin-type-dependent microphase structures of their coalesced samples. Macromolecules 35, 2401–2405 (2002)

    Article  CAS  Google Scholar 

  10. Uyar, T., Rusa, C.C., Hunt, M.A., Aslan, E., Hacaloglu, J., Tonelli, A.E.: Reorganization and Improvement of Bulk Polymers by Processing with Their Cyclodextrin Inclusion Compounds. Polymer 46, 4762–4775 (2005)

    Article  CAS  Google Scholar 

  11. Hunt, M.A., Tonelli, A.E., Balik, C.M.: The effect of water on the solid-state complexation of oligomers with α-cyclodextrin. Polymer 49, 985–991 (2008)

    Article  CAS  Google Scholar 

  12. Hunt, M.A., Rusa, C.C., Tonelli, A.E., Balik, C.M.: Structure, stability of columnar cyclomaltooctaose (γ-cyclodextrin) hydrate. Carbohydr. Res. 340, 1631–1637 (2005)

    Article  CAS  Google Scholar 

  13. Rusa, C.C., Bullions, T.A., Fox, J., Porbeni, F.E., Wang, X., Tonelli, A.E.: Inclusion compound formation with a new columnar cyclodextrin host. Langmuir 18, 10016–10023 (2002)

    Article  CAS  Google Scholar 

  14. Tu, C.-W., Kuo, S.-W., Chang, F.-C.: Supramolecular self-assembly through inclusion complex formation between poly(ethylene oxide-b-N-isopropylacrylamide) block copolymer and α-cyclodextrin. Polymer 50, 2958–2966 (2009)

    Article  CAS  Google Scholar 

  15. Middleton, J.C., Tipton, A.J.: Synthetic biodegradable polymers as orthopedic devices. Biomaterials 21, 2335–2346 (2000)

    Article  CAS  Google Scholar 

  16. Ong, C., Price, F.: Blends of poly(ε-caprolactone) with poly(vinyl chloride). I. Morphology. J. Polym. Sci. 63, 45–58 (1978)

    CAS  Google Scholar 

  17. Tsai, C.-C., Zhang, W.-B., Wang, C.-L., Van Horn, R.M., Graham, M.J., Huang, J., Chen, Y., Guo M, Cheng S.Z.D.: Evidence of formation of site-selective inclusion complexation between β-cyclodextrin and poly(ethylene oxide)-block-poly(propylene oxide)- block-poly(ethylene oxide) copolymers. J. Chem. Phys. 132. doi:10.1063/1.3428769

  18. Zhao, T., Beckham, H.W.: Direct synthesis of cyclodextrin-rotaxanated poly(ethylene glycol)s and their self-diffusion behavior in dilute solution. Macromolecules 36, 9859–9865 (2003)

    Article  CAS  Google Scholar 

  19. Girardeau, T.E., Zhao, T., Leisen, J., Beckham, H.W., Bucknall, D.G.: Solid inclusion complexes of α-cyclodextrin and perdeuterated poly(oxyethylene). Macromolecules 38, 2261–2270 (2005)

    Article  CAS  Google Scholar 

  20. Tonelli, A.E.: Soluble PEG-r-CD-rotaxanes: where on the PEG chains are the permanently threaded r-CDs located and are they mobile?. Macromolecules 41, 4058–4060 (2008)

    Article  CAS  Google Scholar 

Download references

Acknowledgments

We are grateful to the National Textile Center (US Commerce Department), the College of Textiles, and North Carolina State University for their financial and facilities support.

Author information

Authors and Affiliations

  1. Fiber and Polymer Science Program, North Carolina State University, Campus Box 8301, Raleigh, NC, 27695-8301, USA

    Brandon R. Williamson & Alan E. Tonelli

Authors
  1. Brandon R. Williamson
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Alan E. Tonelli
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Alan E. Tonelli.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Williamson, B.R., Tonelli, A.E. Constrained polymer chain behavior observed in their non-stoichiometric cyclodextrin inclusion complexes. J Incl Phenom Macrocycl Chem 72, 71–78 (2012). https://doi.org/10.1007/s10847-011-9940-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10847-011-9940-7

Keywords

Search

Navigation