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Enhancement of the crystallization and thermal stability of polyhydroxybutyrate by polymeric additives

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Abstract

The crystallization and thermal degradation of polyhydroxybutyrate (PHB) blended with a small amount of carboxyl-terminated butadiene acrylonitrile rubber (CTBN) and biocompatible polyvinylpyrrolidone (PVP) are analyzed by differential scanning calorimetry (DSC), dynamic thermogravimetric analysis (TG), gel permeation chromatography (GPC), polarized optical microscope (POM), and wide angle X-ray diffraction (WAXD). From results of DSC, TG, and GPC, it is shown that the presence of PVP or CTBN could affect the crystallization rate, crystallinity, melting temperature, and thermal stability of PHB. The changes of crystal sizes by the added CTBN and PVP are also confirmed by the POM and WAXD analyses. The addition of the 1 wt% PVP or CTBN into PHB can significantly increase the crystallization rate and thermal degradation temperature, and affect the degradation kinetics of PHB due to the steric hindrance effects of the added PVP and CTBN on retarding the degradation reaction. The best improvement of the thermal stability is obtained from the PVP-modified PHB. The method of using CTBN or PVP to improve the thermal stability of PHB is of great processing advantages in industry because it is functional with low purity PHB, henceforth, saves the cost of the purification process.

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References

  1. Mas-Castella J, Urmeneta J, Lafuente R, Navarrete A, Guerrero R. Biodegradation of Poly-[β]-hydroxyalkanoates in anaerobic sediments. Int Biodeterior Biodegrad. 1995;35:155–74.

    Article  CAS  Google Scholar 

  2. Doi Y, Kasuya K, Abe H, Koyama N, Ishiwatari S, Takagi K, Yoshida Y. Evaluation of biodegradabilities of biosynthetic and chemosynthetic polyesters in river water. Polym Degrad Stab. 1996;51:281–6.

    Article  CAS  Google Scholar 

  3. Yoon JS, Jung HW, Kim MN, Park ES. Diffusion coefficient and equilibrium solubility of water molecules in biodegradable polymers. J Appl Polym Sci. 2000;77:1716–22.

    Article  CAS  Google Scholar 

  4. Iwata T, Shiromo M, Doi Y. Surface structures of poly[(R)-3-hydroxybutyrate] and its copolymer single crystals before and after enzymatic degradation with an extracellular PHB depolymerase. Macro Chem Phys. 2002;203:1309–16.

    Article  CAS  Google Scholar 

  5. Doi Y, Mukai K, Kasuya K, Yamada K. Biodegradation of biosynthetic and chemosynthetic polyhydroxyalkanoates. In: Doi Y, Fukuda K, editors. Biodegradable plastics and polymers. Amsterdam: Elsevier; 1994. p. 39–51.

    Google Scholar 

  6. Kumagai Y, Kanesawa Y, Doi Y. Enzymatic degradation of microbial poly(3-hydroxybutyrate) films. Makromol Chem. 1992;193:53–7.

    Article  CAS  Google Scholar 

  7. Tomasi G, Scandola M, Briese BH, Jendrossek D. Enzymatic degradation of bacterial poly(3-hydroxybutyrate) by a depolymerase from Pseudomonas lemoignei. Macromolecules. 1996;29:507–13.

    Article  CAS  Google Scholar 

  8. Koyama N, Doi Y. Effects of solid-state structures on the enzymatic degradability of bacterial poly(hydroxyalkanoic acids). Macromolecules. 1997;30:826–32.

    Article  CAS  Google Scholar 

  9. Zhao K, Deng Y, Chen GQ. Effects of surface morphology on the biocompatibility of polyhydroxyalkanoates. Biochem Eng J. 2003;16:115–23.

    Article  CAS  Google Scholar 

  10. Zheng Z, Bei FF, Tian HL, Chen GQ. Effects of crystallization of polyhydroxyalkanoate blend on surface physicochemical properties and interactions with rabbit articular cartilage chondrocytes. Biomaterials. 2005;26:3537–48.

    Article  CAS  Google Scholar 

  11. Chen C, Fei B, Peng S, Zhuang Y, Dong L, Feng Z. Nonisothermal crystallization and melting behavior of poly(3-hydroxybutyrate) and maleated poly(3-hydroxybutyrate). Eur Polym J. 2002;38:1663–70.

    Article  CAS  Google Scholar 

  12. Wang L, Zhu W, Wang X, Chen X, Chen GQ, Xu K. Processability modifications of poly(3-hydroxybutyrate) by plasticizing, blending, and stabilizing. J Appl Polym Sci. 2008;107:166–73.

    Article  CAS  Google Scholar 

  13. Zhao Q, Cheng G, Song C, Zeng Y, Tao J, Zhang L. Crystallization behavior and biodegradation of poly(3-hydroxybutyrate) and poly(ethylene glycol) multiblock copolymers. Polym Degrad Stab. 2006;91:1240–6.

    Article  CAS  Google Scholar 

  14. Lee HK, Ismail J, Kammer HW, Bakar MA. Melt reaction in blends of poly(3-hydroxybutyrate) (PHB) and epoxidized natural rubber (ENR-50). J Appl Polym Sci. 2005;95:113–29.

    Article  CAS  Google Scholar 

  15. Kaito A. Unique orientation textures formed in miscible blends of poly(vinylidene fluoride) and poly[(R)-3-hydroxybutyrate]. Polymer. 2006;47:3548–56.

    Article  CAS  Google Scholar 

  16. El-Taweel SH, Stoll B, Hohne GWH, Mansour AA, Seliger H. Stress-strain behavior of blends of bacterial polyhydroxybutyrate. J Appl Polym Sci. 2004;94:2528–37.

    Article  CAS  Google Scholar 

  17. Stefani PM, Ruseckaite RA, Vázquez A. Poly(3-hydroxybutyrate-co-11 mass% 3-hydroxyvaleate) molded part during the solidification step. J Therm Anal Calorim. 2009;95:305–12.

    Article  CAS  Google Scholar 

  18. Malinova L, Brozek J, Mixtures poly((R)-3-hydroxybutyrate) and poly(L-lactic acid) subjected to DSC, J. Therm. Anal. Calorim. 2010; Published online: 28 October 2010.

  19. Rodrigues JAFR, Parra DF, Lugao AB. Crystallization on Films of PHB/PEG Blends. J Therm Anal Calorim. 2005;79:379–81.

    Article  CAS  Google Scholar 

  20. Bahari K, Mitomo H, Enjoji T, Yoshii F. Degradability of poly(3-hydroxybutyrate) and its copolymer grafted with styrene by radiation. Polym Degrad Stab. 1998;61:245–52.

    Article  CAS  Google Scholar 

  21. Chen C, Peng S, Fei B, Zhuang Y, Dong L, Feng Z, Chen S, Xia H. Synthesis and characterization of maleated poly(3-hydroxybutyrate). J Appl Polym Sci. 2003;88:659–68.

    Article  CAS  Google Scholar 

  22. Chen C, Fei B, Peng S, Zhuang Y, Dong L, Feng Z. The kinetics of the thermal decomposition of poly(3-hydroxybutyrate) and maleated poly(3-hydroxybutyrate). J Appl Polym Sci. 2002;84:1789–96.

    Article  CAS  Google Scholar 

  23. Hong SG, Lin YC. Improvement of the thermal stability of polyhydroxybutyrates by grafting with maleic anhydride by different methods: differential scanning calorimetry, thermogravimetric analysis, and gel permeation chromatography. J Appl Polym Sci. 2008;110:2718–26.

    Article  CAS  Google Scholar 

  24. Hong SG, Lin YC. Crystallization and degradation behaviors of treated polyhydroxybutyrates. React Funct Polym. 2008;68:1516–23.

    Article  CAS  Google Scholar 

  25. Grassie N, Marray EJ, Holmes PA. The thermal degradation of poly(-(D)-β-hydroxybutyric acid): part 1—identification and quantitative analysis of products. Polym Degrad Stab. 1984;6:47–61.

    Article  CAS  Google Scholar 

  26. Grassie N, Marray EJ, Holmes PA. The thermal degradation of poly(-(D)-β-hydroxybutyric acid): part 2—changes in molecular weight. Polym Degrad Stab. 1984;6:95–103.

    Article  CAS  Google Scholar 

  27. Lee WK, Iwata T, Abe H, Doi Y. Studies on the enzymatic degradation of solution-grown lamellar crystals of poly[(r)-3-hydroxybutyrate]: defects in crystals. Macromolecules. 2000;33:9535–41.

    Article  CAS  Google Scholar 

  28. Gunaratne LWMK, Shanks RA, Amarasinghe G. Thermal history effects on crystallization and melting of poly(3-hydroxybutyrate). Thermochim Acta. 2004;423:127–35.

    Article  CAS  Google Scholar 

  29. Gunaratne LWMK, Shanks RA. Melting and thermal history of poly(hydroxybutyrate-co-hydroxyvalerate) using step-scan DSC. Thermochim Acta. 2005;430:183–90.

    Article  CAS  Google Scholar 

  30. Liu T, Petermann J. Multiple melting behavior in isothermally cold-crystallized isotactic polystyrene. Polymer. 2001;42:6453–61.

    Article  CAS  Google Scholar 

  31. Kopinke ED, Mackenzie K. Mechanistic aspects of the thermal degradation of poly(lactic acid) and poly([β]-hydroxybutyric acid). J Anal Appl Pyrol. 1997;40–41:43–53.

    Article  Google Scholar 

  32. Kopinke FD, Remmler M, Mackenzie K. Thermal decomposition of biodegradable polyesters—I: poly([β]-hydroxybutyric acid). Polym Degrad Stab. 1996;52:25–38.

    Article  CAS  Google Scholar 

  33. Valappil SP, Boccaccini AR, Bucke C, Roy I. Polyhydroxyalkanoates in Gram-positive bacteria: insights from the genera Bacillus and Streptomyces. Antonie Van Leeuwenhoek. 2007;91:1–17.

    Article  CAS  Google Scholar 

  34. Kim KJ, Doi Y, Abe HA. Effects of residual metal compounds and chain-end structure on thermal degradation of poly(3-hydroxybutyric acid). Polym Degrad Stab. 2006;91:769–77.

    Article  CAS  Google Scholar 

  35. Ahmed EH, Rainer S, Ekkehard S, Gert M, Riemschneider M. Effect of melt processing on crystallization behavior and rheology of poly(3-hydroxybutyrate) (phb) and its blends. Macromol Mater Eng. 2002;287:363–72.

    Article  Google Scholar 

  36. Canetti M, Urso M, Sadocco P. Influence of the morphology and of the supermolecular structure on the enzymatic degradation of bacterial poly(3-hydroxybutyrate). Polymer. 1999;40:2587–94.

    Article  CAS  Google Scholar 

  37. Tang W, Li XG, Yan D. Thermal decomposition kinetics of thermotropic copolyesters made from trans-p-hydroxycinnamic acid and p-hydroxybenzoic acid. J Appl Polym Sci. 2004;91:445–54.

    Article  CAS  Google Scholar 

  38. Flynn JH, Wall LA. General treatment of the thermogravimetry of polymers. J Res Natl Bur Stand. 1966;70A:487–523.

    Google Scholar 

  39. Ozawa T. A new method of analyzing thermogravimetric data. Bull Chem Soc Jpn. 1965;38:1881–6.

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Department of Chemical Engineering and Materials Science, Yuan-Ze University, Chung-Li 320, Taiwan

    Shinn-Gwo Hong, Tsung-Kai Gau & Shih-Che Huang

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  1. Shinn-Gwo Hong
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  2. Tsung-Kai Gau
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Correspondence to Shinn-Gwo Hong.

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Hong, SG., Gau, TK. & Huang, SC. Enhancement of the crystallization and thermal stability of polyhydroxybutyrate by polymeric additives. J Therm Anal Calorim 103, 967–975 (2011). https://doi.org/10.1007/s10973-010-1180-3

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  • DOI: https://doi.org/10.1007/s10973-010-1180-3

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