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Crystallization and Enzymatic Degradation of Maleic Acid-Grafted Poly(butylene adipate-co-terephthalate)/Organically Modified Layered Zinc Phenylphosphonate Nanocomposites

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Biodegradable nanocomposites were successfully synthesized using the maleic acid-grafted poly(butylene adipate-co-terephthalate) (g-PBAT) and organically modified layered zinc phenylphosphonate (m-PPZn), containing covalent linkages between g-PBAT and m-PPZn. Differential scanning calorimetry, wide-angle X-ray diffraction (WAXD), and transmission electron microscopy (TEM) were used to determine the crystallization behavior and morphology of g-PBAT/m-PPZn nanocomposites. The isothermal crystallization kinetics of g-PBAT/m-PPZn nanocomposites was determined using the Avrami equation. It was found that the half-time for the crystallization of the neat g-PBAT matrix is larger than that of g-PBAT/m-PPZn nanocomposites. This result suggests that the incorporation of m-PPZn can improve the crystallization rate of nanocomposites. The WAXD and TEM data illustrate that most of the m-PPZn layered materials are partially intercalated or exfoliated in the g-PBAT matrix. As the enzyme, lipase from Pseudomonas sp. was used for the enzymatic degradation tests. The degradation rates of the neatly fabricated g-PBAT copolymers using the heat pressing technique increase in the order of g-PBAT-80 > g-PBAT-50 > g-PBAT-20. The growing degradation rate of g-PBAT-80 is due to the growing amount of the adipate acid group and the increasing chain flexibility of the polymer backbone. Moreover, the increasing loading of m-PPZn enhances the weight loss of nanocomposites, suggesting that the existence of m-PPZn enhances the degradation of g-PBAT copolymers. The degradation rate of the freeze-drying samples containing a highly porous structure is greater than those prepared using the heat pressing technique.

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  1. 1.

    Tserki V, Matzinos P, Pavlidou E, Vachliotis D, Panayiotou C (2006) Biodegradable aliphatic polyesters. Part I. properties and biodegradation of poly(butylene succinate-co-butylene adipate). Polym Degrad Stab 91:367

  2. 2.

    Muller RJ, Kleeberg I, Deckwer WD (2001) Biodegradation of polyesters containing aromatic constituents. J Biotech 86:87

  3. 3.

    Gan Z, Kuwabara K, Yamamoto M, Abe H, Doi Y (2004) Solid-state structures and thermal properties of aliphatic–aromatic poly(butylene adipate-co-butylene terephthalate) copolyesters. Polym Degrad Stab 83:289

  4. 4.

    Zhao L, Gan Z (2006) Effect of copolymerized butylene terephthalate chains on polymorphism and enzymatic degradation of poly(butylene adipate). Polym Degrad Stab 91:2429

  5. 5.

    Shi XQ, Ito H, Kikutani T (2005) Characterization on mixed-crystal structure and properties of poly (butylene adipate-co-terephthalate) biodegradable fibers. Polymer 46:11442

  6. 6.

    Kijchavengkul T, Auras R, Rubino M, Alvarado E, Montero JRC, Rosales JM (2010) Atmospheric and soil degradation of aliphaticearomatic polyester films. Polym Degrad Stab 95:99

  7. 7.

    Nikolic MS, Djonlagic J (2001) Synthesis and characterization of biodegradable poly(butylene succinate-co-butylene adipate)s. Polym Degrad Stab 74:263

  8. 8.

    Ojijo V, Cele H, Sinha Ray S (2011) Morphology and properties of polymer composites based on biodegradable polylactide/poly[(butylene succinate)-co-adipate] blend and nanoclay. Macromol Mater Eng 296:865

  9. 9.

    Liu B, Bhaladhare S, Zhan P, Jiang L, Zhang J, Liu L, Hotchkiss AT (2011) Morphology and properties of thermoplastic sugar beet pulp and poly(butylene adipate-co-terepthalate) blends. Ind Eng Chem Res 50:13859

  10. 10.

    Rodrigues BVM, Silva AS, Melo GFS, Vasconscellos LMR, Marciano FR, Lobo AO (2016) Influence of low contents of superhydrophilic MWCNT on the properties and cell viability of electrospun poly (butylene adipate-co-terephthalate) fibers. Mater Sci Eng C 59:782

  11. 11.

    Moustafa H, Guizani C, Dupont C, Martin V, Jeguirim M, Dufresne A (2017) Utilization of torrefied coffee grounds as reinforcing agent to produce high-quality biodegradable PBAT composites for food packaging applications. ACS Sustain Chem Eng 5:1906

  12. 12.

    Pan P, Liang Z, Cao A, Inoue Y (2009) Layered metal phosphonate reinforced poly(l-lactide) composites with a highly enhanced crystallization rate. ACS Appl Mat Interfaces 1:402

  13. 13.

    Xu T, Wang Y, He D, Xu Y, Li Q, Shen C (2014) Nucleation effect of layered metal phosphonate on crystallization of isotactic polypropylene. Polym Test 34:131

  14. 14.

    Yu F, Pan P, Nakamura N, Inoue Y (2011) Nucleation effect of layered metal phosphonate on crystallization of bacterial poly[(3-hydroxybutyrate)-co-(3-hydroxyhexanoate)]. Macromol Mater Eng 296:103

  15. 15.

    Wang HT, Wang JM, Wu TM (2019) Synthesis and characterization of biodegradable aliphatic-aromatic nanocomposites fabricated using maleic acid-grafted poly(butylene adipate-co-terephthalate) and organically modified layered zinc phenylphosphonate. Polym Int 68:1531

  16. 16.

    Poojary DM, Clearfield A (1995) Coordinative intercalation of alkylamines into layered zinc phenylphosphonate. Crystal structures from X-ray powder diffraction data. J Am Chem Soc 117:11278

  17. 17.

    Zhang Y, Scott KJ, Clearfield A (1995) Intercalation of alkylamines into dehydrated and hydrated phenylphosphonates. J Mater Chem 5:315

  18. 18.

    Avrami M (1940) Kinetics of phase change. II Transformation‐time relations for random distribution of nuclei. J Chem Phys 8:212

  19. 19.

    Avrami M (1941) Granulation, phase change, and microstructure kinetics of phase change: III. J Chem Phys 9:177

  20. 20.

    Chen YA, Chen EC, Wu TM (2015) Organically-modified layered zinc phenylphosphonate reinforced stereocomplex-type poly(lactic acid) nanocomposites with the highly enhanced mechanical properties and degradability. J Mater Sci 50:7770

  21. 21.

    Chen YA, Chen EC, Wu TM (2016) Lamellae evolution of stereocomplex-type poly(lactic acid)/organically-modified layered zinc phenylphosphonate nanocomposites induced by isothermal crystallization. Materials 9:159

  22. 22.

    Alamo RG, Mandelkern L (1991) Crystallization kinetics of random ethylene copolymers. Macromolecules 24:6480

  23. 23.

    Chen YA, Wu TM (2014) Crystallization kinetics of poly(1,4-butylene adipate) with stereocomplexed poly(lactic acid) serving as a nucleation agent. Ind Eng Chem Res 53:16689

  24. 24.

    Hocking PJ, Marchessault RH, Timmins MR, Lenz RW, Fuller RC (1996) Enzymatic degradation of single crystals of bacterial and synthetic poly(β-hydroxybutyrate). Macromolecules 29:2472

  25. 25.

    Ciou CY, Li SY, Wu TM (2014) Morphology and degradation behavior of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/layered double hydroxides composites. Eur Polym J 59:136

  26. 26.

    Bikiaris DN (2013) Nanocomposites of aliphatic polyesters: an overview of the effect of different nanofillers on enzymatic hydrolysis and biodegradation of polyesters. Polym Degrad Stab 98:1908

  27. 27.

    Bikiaris DN, Nianias NP, Karagiannidou EG, Docoslis A (2012) Effect of different nanoparticles on the properties and enzymatic hydrolysis mechanism of aliphatic polyesters. Polym Degrad Stab 97:2077

  28. 28.

    Chen YA, Kuo DL, Chen EC, Wu TM (2017) Enhanced enzymatic degradation in nanocomposites of various organically-modified layered zinc phenylphosphonates and poly (butylene succinate-co-adipate). J Polym Res 24:212

  29. 29.

    Kuo DL, Wu TM (2019) Crystallization behavior and morphology of hexadecylamine-modified layered zinc phenylphosphonate and poly(butylene succinate-co-adipate) composites with controllable biodegradation rates. J Polym Environ 27:10

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This work is supported by the Ministry of Science and Technology (MOST) under Grant MOST 107-2221-E-005-020 and the Ministry of Education under the project of Innovation and Development Center of Sustainable Agriculture (IDCSA).

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Correspondence to Tzong-Ming Wu.

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Wang, H., Chen, E. & Wu, T. Crystallization and Enzymatic Degradation of Maleic Acid-Grafted Poly(butylene adipate-co-terephthalate)/Organically Modified Layered Zinc Phenylphosphonate Nanocomposites. J Polym Environ 28, 834–843 (2020). https://doi.org/10.1007/s10924-019-01647-0

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  • Composites
  • Crystallization behavior
  • Enzymatic degradation