Crosslinking as an Efficient Tool for Decreasing Moisture Sensitivity of Biobased Nanocomposite Films
Jari Vartiainen, Ali Harlin
DOI: 10.4236/msa.2011.25045   PDF    HTML     6,910 Downloads   13,754 Views   Citations

Abstract

Chitosan-nanoclay bio-hybrid films were successfully crosslinked with glutaraldehyde, genipin and glyoxal. Moisture sensitivity of films decreased as a result of crosslinking which led to improved barrier properties against water vapor and oxygen. Films containing chitosan (6.6 g/m2) with genipin (3.3 g/m2) and nanoclay (6.6 g/m2) had water vapor transmission rate of 72 g × 100 µm/(m2 × 24 h) which was 34% lower as compared to pure chitosan and 30% lower as compared to chitosan/nanoclay without crosslinkers. Glyoxal induced crosslinking resulted in 92% reduction in oxygen transmission rate at 80% relative humidity as compared to pure chitosan films. Oxygen transmission through glyoxal (3.3 g/m2) treated chitosan/nanoclay film was 2.8 cm3 × 100 µm/(m2 × 24 h) which was 53% lower as compared to chitosan/nanoclay without crosslinkers. In addition, nanoclay and especially glyoxal crosslinking prevented the water vapor sorption of chitosan considerably. Crosslinking may be used as an efficient tool for enhancing the exploitability of naturally hydrophilic biopolymers towards new high-value applications, such as food packaging.

Share and Cite:

Vartiainen, J. and Harlin, A. (2011) Crosslinking as an Efficient Tool for Decreasing Moisture Sensitivity of Biobased Nanocomposite Films. Materials Sciences and Applications, 2, 346-354. doi: 10.4236/msa.2011.25045.

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1] [1] T. Lan, P. D. Kaviratna and T. J. Pinnavaia, “On the Nature of Polyimide-Clay Hybrid Composites,” Chemistry of Materials, Vol. 6, No. 5, May 1994, pp. 573-575. doi:10.1021/cm00041a002
[2] P. B. Messersmith and E. P. Giannelis, “Synthesis and Barrier Properties of Poly(?-Caprolactone)-Layered Silicate Nanocomposites,” Journal of Polymer Science Part A: Polymer Chemistry, Vol. 33, No. 7, May 1995, pp. 1047-1057. doi:10.1002/pola.1995.080330707
[3] K. Yano, A. Usuki and A. Okada, “Synthesis and Properties of Polyimide-Clay Hybrid Films,” Journal of Polymer Science Part A: Polymer Chemistry, Vol. 35, No. 11, August 1997, pp. 2289-2294. doi:10.1002/(SICI)1099-0518(199708)35:11<2289::AID-POLA20>3.0.CO;2-9
[4] D. Depan, B. Kumar and R. P. Singh, “Preparation and Characterization of Novel Hybrid of Chitosan-g-PDMS and Sodium Montmorillonite,” Journal of Biomedical Materials Research Part B: Applied Biomaterials, Vol. 84, No. 1, January 2008, pp. 184-190. doi:10.1002/jbm.b.30860
[5] X. Wang, Y. Du, J. Yang, X. Wang, X. Shi and Y. Hu, “Preparation, Characterization and Antimicrobial Activity of Chitosan/Layered Silicate Nanocomposites,” Polymer, Vol. 47, No. 19, September 2006, pp. 6738-6744. doi:10.1016/j.polymer.2006.07.026
[6] C. Tang, N. Chen, Q. Zhang, K. Wang, Q. Fu and X. Zhang, “Preparation and Properties of Chitosan Nanocomposites with Nanofillers of Different Dimensions,” Polymer Degradation and Stability, Vol. 94, No. 1, January 2009, pp. 124-131.
[7] X. Wang, Y. Du, J. Luo, B. Lin and J. F. Kennedy, “Chitosan/Organic Rectorite Nanocomposite Films: Structure, Characteristic and Drug Delivery Behaviour,” Carbohydrate Polymers, Vol. 69, No. 1, May 2007, pp. 41-49. doi:10.1016/j.carbpol.2006.08.025
[8] J. Vartiainen, M. Tuominen and K. N?ttinen, “Bio-Hybrid Nanocomposite Coatings from Sonicated Chitosan and Nanoclay, Journal of Applied Polymer Science, Vol. 116, No. 6, June 2010, pp. 3638-3647.
[9] J. M. Lagarón and A. Fendler, “High Water Barrier Nanobiocomposites of Methyl Cellulose and Chitosan for Film and Coating Applications,” Journal of Plastic Film and Sheeting, Vol. 25, No. 1, January 2009, pp. 47-59.
[10] E. Dunkerley and D. Schmidt, “Effects of Composition, Orientation and Temperature on the O2 Permeability of Model Polymer/Clay Nanocomposites,” Macromolecules, Vol. 43, No. 24, December 2010, pp. 10536-10544. doi:10.1021/ma1018846
[11] G. A. F. Roberts and K. E. Taylor, “Chitosan Gels, 3: The Formation of Gels by Reaction of Chitosan with Glutaraldehyde,” Die Makromolekulare Chemie, Vol. 190, No. 5, May 1989, pp. 951-960. doi:10.1002/macp.1989.021900504
[12] R. A. A. Muzzarelli, “Genipin-Crosslinked Chitosan Hydrogels as Biomedical and Pharmaceutical Aids,” Carbohydrate Polymers, Vol. 77, No. 22, pp. 1-9.
[13] J. Z. Knaul, S. M. Hudson and K. A. M. Creber, “Cross- linking of Chitosan Fibers with Dialdehydes: Proposal of a New Reaction Mechanism,”Journal of Polymer Science Part B: Polymer Physics, Vol. 37, No. 1, June 1999, pp. 1079-1094. doi:10.1002/(SICI)1099-0488(19990601)37:11<1079::AID-POLB4>3.0.CO;2-O
[14] Y. Yuan, B. M. Chesnutt, G. Utturkar, W. O. Haggard, Y. Yang, J. L. Ong and J. D. Bumgardner, “The Effect of Cross-Linking of Chitosan Microspheres with Genipin on Protein Release,” Carbohydrate Polymers, Vol. 68, No. 3, April 2007, pp. 561-567. doi:10.1016/j.carbpol.2006.10.023
[15] F. L. Mi, S. S. Shyu and C. K. Peng, “Characterization of Ring-Opening Polymerization of Genipin and pH-Depen- dent Cross-Linking Reactions Between Chitosan and Ge- nipin,” Journal of Polymer Science Part A: Polymer Che- mistry, Vol. 43, No. 10, May 2005, pp. 1985-2000. doi:10.1002/pola.20669
[16] J. Vartiainen, T. Tammelin, J. Pere, U. Tapper and A. Harlin, “Biohybrid Barrier Films from Fluidized Pectin and Nanoclay,” Carbohydrate Polymers, Vol. 82, No. 3, October 2010, pp. 989-996. doi:10.1016/j.carbpol.2010.06.031
[17] G. Kumar, J. F. Bristow, P. J. Smith and G. F. Payne, “Enzymatic Gelation of the Natural Polymer Chitosan,” Polymer, Vol. 41, No. 6, March 2000, pp. 2157-2168. doi:10.1016/S0032-3861(99)00360-2
[18] S. F. Wang, L. Shen, Y. J. Tong, L. Chen, I. Y. Phang, P. Q. Lim and T. X. Liu, “Biopolymer Chitosan/Mont- morillonite Nanocomposites: Preparation and Characterization,” Polymer Degradation and Stability, Vol. 90, No. 1, October 2005, pp. 123-131. doi:10.1016/j.polymdegradstab.2005.03.001
[19] M. M. Malwitz, S. Lin-Gibson, E. K. Hobble, P. D. Butler, G. Schmidt, “Orientation of Platelets in Multilayered Nanocomposite Polymer Films,” Journal of Polymer Science Part B: Polymer Physics, Vol. 41, No. 24, December 2003, pp. 3237-3248.
[20] G. L. Clark and A. F. Smith, “X-Ray Diffraction Studies of Chitin, Chitosan and Derivatives,” Journal of Physical Chemistry, Vol. 40, No. 7, 1936, pp. 863-879. doi:10.1021/j150376a001
[21] M. Darder, M. Colilla and E. Ruiz-Hitzky, “Biopolymer-Clay Nanocomposites Based on Chitosan Intercalated in Montmorillonite,” Chemistry of Materials, Vol. 15, No. 20, October 2003, pp. 3774-3780. doi:10.1021/cm0343047
[22] M. Darder, M. Colilla and E. Ruiz-Hitzky, “Chitosan- Clay Nanocomposites: Application as Electrochemical Sensors,” Applied Clay Science, Vol. 28, No. 1-4, pp. 199- 208.
[23] H.-C. Liang, W.-H. Chang, K.-J. Lin and H.-W. Sung, “Genipin-Crosslinked Gelatin Microspheres as a Drug Carrier for Intramuscular Administration: In vitro and in vivo studies,” Journal of Biomedical Materials Research Part A, Vol. 65A, No. 2, May 2003, pp. 271-282. doi:10.1002/jbm.a.10476
[24] J. D. Wind, S. M. Sirard, D. R. Paul, P. F. Green, K. P. Johnston and W. J. Koros, “Relaxation Dynamics of CO2 Diffusion, Sorption, and Polymer Swelling for Plasticized Polyimide Membranes,” Macromolecules, Vol. 36, No. 17, August 2003, pp. 6442-6448. doi:10.1021/ma034359u
[25] C. Thellen, C. Orroth, D. Froio, D. Ziegler, J. Lucciarini, R. Farrell, N. A. D’souza and J. A. Ratto, “Influence of Montmorillonite Layered Silicate on Plasticized Poly (L-Lactide) Blown Films,” Polymer, Vol. 46, No. 25, November 2005, pp. 11716-11727. doi:10.1016/j.polymer.2005.09.057
[26] C. M. Roland and C. A. Aronson, “Crystallization of Polydimethylsiloxane End-Linked Networks,” Polymer Bulletin, Vol. 45, No. 4-5, December 2000, pp. 439-445. doi:10.1007/s002890070019
[27] O. O. Christopher and M. Lerner, “Nanocomposites and Intercalation Compound, Encyclopedia of Physical Science and Technology,” 3rd Edition, Academic Press, San Diego, 2001.
[28] Z. Ke and B. Yongping, “Improve the Gas Barrier Property of PET Film with Montmorillonite by In Situ Interlayer Polymerization,” Materials Letters, Vol. 59, No. 27, November 2005, pp. 3348-3351. doi:10.1016/j.matlet.2005.05.070
[29] J. Lange and Y. Wyser, “Recent Innovations in Barrier Technologies for Plastic Packaging—A Review,” Packaging Technology and Science, Vol. 16, No. 4, July/Au- gust 2003, pp. 149-158.
[30] S. S. Ray, K. Yamada, M. Okamoto and K. Ueda, “New Polylactide-Layered Silicate Nanocomposites. 2. Concurrent Improvements of Material Properties, Biodegradability and Melt Rheology,” Polymer, Vol. 44, No. 3, February 2003, pp. 857-866.
[31] J. H. Chang, Y. Uk-An and G. S. Sur, “Poly(Lactic Acid) Nanocomposites with Various Organoclays. I. Thermo- mechanical Properties, Morphology, and Gas Permeability,” Journal of Polymer Science Part B: Polymer Physics, Vol. 41, No. 1, January 2003, pp. 94-103. doi:10.1002/polb.10349
[32] K. C. Gupta and F. H. Jabrail, “Glutaraldehyde and Glyoxal Cross-Linked Chitosan Microspheres for Controlled Delivery of Centchroman,” Carbohydrate Research, Vol. 341, No. 6, May 2006, pp. 744-756. doi:10.1016/j.carres.2006.02.003

Copyright © 2024 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.