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Toughened Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/Epoxidized Natural Rubber Blends Fabricated by Dynamic Vulcanization and Interfacial Compatibilization

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Abstract

Biodegradable polymers, particularly Polyhydroxyalkanoates (PHAs) and their derivatives, have garnered increasing attention across diverse industries owing to their distinct advantages such as bio-based sourcing, biocompatibility, and impressive biodegradability performance. Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) is one of the most attractive members of PHAs with a great potential to replace conventional non-biodegradable polymers. However, one critical drawback restricting PHBV usage is its thermal instability, which could bring about a narrow processing window, especially for conventional melt processing methods such as injection molding. Moreover, the high crystallinity and slow nucleation rate make PHBV brittle, leading to poor mechanical performance. This study incorporated epoxidized natural rubbers (ENR-25 and ENR-50) into PHBV through a melt blending process to enhance PHBV toughness and flexibility. Incorporation of 5wt% polybutadiene grafted maleic anhydride (PB-g-MA) as a compatibilizer notably enhances mechanical properties. Furthermore, the study introduces the concept of thermoplastic vulcanizate (TPV) through melt blending using dynamic vulcanization (DV) to enhance mechanical properties, particularly the toughness of the 70/30 PHBV/ENR blends, identified as the optimal blending ratio based on prior research. The resulting blend vulcanizate (PHBV/ENRv) exhibits toughness values of 63.0 ± 14.8 J m− 1 and 24.4 ± 2.8 J m− 1 for blends with ENRv-25 and ENRv-50, respectively. These findings hold promise for advancing the design and development of biodegradable polymer blend systems, with a focus on enhancing processability and mechanical performance.

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References

  1. Gironi F, Piemonte V (2011) Bioplastics and petroleum-based plastics: strengths and weaknesses. Energy sources, part a: recovery, utilization. Environ Eff 33(21):1949–1959. https://doi.org/10.1080/15567030903436830

    Article  CAS  Google Scholar 

  2. Bhatt R, Shah D, Patel KC, Trivedi U (2008) PHA–rubber blends: synthesis, characterization and biodegradation. Bioresour Technol 99(11):4615–4620. https://doi.org/10.1016/j.biortech.2007.06.054

    Article  CAS  PubMed  Google Scholar 

  3. Lenz RW, Marchessault RH (2005) Bacterial polyesters: Biosynthesis, Biodegradable Plastics and Biotechnology. Biomacromolecules 6(1):1–8. https://doi.org/10.1021/bm049700c

    Article  CAS  PubMed  Google Scholar 

  4. Anderson AJ, Dawes EA (1990) Occurrence, metabolism, metabolic role, and industrial uses of bacterial polyhydroxyalkanoates. Microbiol Rev 54(4):450–472. https://doi.org/10.1128/mr.54.4.450-472.1990

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  5. Bugnicourt E, Cinelli P, Lazzeri A, Alvarez VA, Polyhydroxyalkanoate (PHA) (eds) (2014) : Review of synthesis, characteristics, processing and potential applications in packaging. https://doi.org/10.3144/expresspolymlett.2014.82

  6. Yeo JCC, Muiruri JK, Thitsartarn W, Li Z, He C (2018) Recent advances in the development of biodegradable PHB-based toughening materials: approaches, advantages and applications. Mater Sci Engineering: C 92:1092–1116. https://doi.org/10.1016/j.msec.2017.11.006

    Article  CAS  Google Scholar 

  7. Tomano N, Boondamnoen O, Aumnate C, Potiyaraj P (2022) Enhancing impact resistance and biodegradability of PHBV by melt blending with ENR. Sci Rep 12(1):22633. https://doi.org/10.1038/s41598-022-27246-z

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  8. Kanabenja W, Passarapark K, Subchokpool T, Nawaaukkaratharnant N, Román AJ, Osswald TA et al (2022) 3D printing filaments from plasticized Polyhydroxybutyrate/Polylactic acid blends reinforced with hydroxyapatite. Additive Manuf 59. https://doi.org/10.1016/j.addma.2022.103130

  9. Jiratchaya SW, Kanabenja; Nichaphat P, Chuanchom A, Pranut (2022) Potiyaraj. Polyhydroxybutyrate/polylactic acid blends: An aiternative feedstock for 3D printed bone scaffold model. Journal of Physics: Conference Series. https://doi.org/10.1088/1742-6596/2175/1/012021

  10. Kuntanoo K, Promkotra S, Kaewkannetra P (2013) Biodegradation of polyhydroxybutyrate-co-hydroxyvalerate (PHBV) blended with natural rubber in soil environment. Int Sci Index 7:12

    Google Scholar 

  11. Potiyaraj NTOBCAP (2022) Development of green materials from ENR-25/PHBV blends: Curing characteristics and mechanical performance. Journal of Physics: Conference Series. https://doi.org/10.1088/1742-6596/2175/1/012026

  12. Tanjung FA, Hassan A, Hasan M (2015) Use of epoxidized natural rubber as a toughening agent in plastics. J Appl Polym Sci 132(29). https://doi.org/10.1002/app.42270

  13. Parulekar Y, Mohanty AK (2006) Biodegradable toughened polymers from renewable resources: blends of polyhydroxybutyrate with epoxidized natural rubber and maleated polybutadiene. Green Chem 8(2):206–213. https://doi.org/10.1039/B508213G

    Article  CAS  Google Scholar 

  14. Liang J, Li R (2000) Rubber toughening in polypropylene: a review. J Appl Polym Sci 77(2):409–417. https://doi.org/10.1002/(SICI)1097-4628(20000711)77:2<409::AID-APP18>3.0.CO;2-N

    Article  CAS  Google Scholar 

  15. Holden G, Bishop E, Legge NR (1969) Thermoplastic elastomers. Journal of Polymer Science Part C: Polymer Symposia: Wiley Online Library; pp 37–57

  16. De S, Bhowmick AK (1990) Thermoplastic elastomers from rubber-plastic blends. Ellis Horwood Limited

  17. Zhao X, Ji K, Kurt K, Cornish K, Vodovotz Y (2019) Optimal mechanical properties of biodegradable natural rubber-toughened PHBV bioplastics intended for food packaging applications. Food Packaging Shelf Life 21:100348. https://doi.org/10.1016/j.fpsl.2019.100348

    Article  Google Scholar 

  18. Zhao X, Cornish K, Vodovotz Y (2019) Synergistic mechanisms underlie the peroxide and coagent improvement of natural-rubber-toughened poly (3-hydroxybutyrate-co-3-hydroxyvalerate) mechanical performance. Polymers 11(3):565. https://doi.org/10.3390/polym11030565

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  19. Zhao X, Venoor V, Koelling K, Cornish K, Vodovotz Y (2019) Bio-based blends from poly (3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) and natural rubber for packaging applications. J Appl Polym Sci 136(15):47334. https://doi.org/10.1002/app.47334

    Article  CAS  Google Scholar 

  20. Shahroodi Z, Katbab AA (2022) Preparation and characterization of peroxide-based dynamically vulcanized thermoplastic elastomer of poly (lactic acid)/chloroprene rubber. Polym Eng Sci 62(5):1485–1495. https://doi.org/10.1002/pen.25937

    Article  CAS  Google Scholar 

  21. Dutta S, Sengupta S, Chanda J, Das A, Wiessner S, Ray SS, Bandyopadhyay A (2020) Distribution of nanoclay in a new TPV/nanoclay composite prepared through dynamic vulcanization. Polym Test 83:106374. https://doi.org/10.1016/j.polymertesting.2020.106374

    Article  CAS  Google Scholar 

  22. Van Dommelen J, Brekelmans W, Baaijens F (2003) Micromechanical modeling of particle-toughening of polymers by locally induced anisotropy. Mech Mater 35(9):845–863. https://doi.org/10.1016/S0167-6636(02)00307-1

    Article  Google Scholar 

  23. Tomano N, Boondamnoen O, Aumnate C, Potiyaraj P (2022) Enhancing impact resistance and biodegradability of PHBV by melt blending with ENR. Sci Rep 12(1):22633

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  24. Scandola M, Focarete ML, Adamus G, Sikorska W, Baranowska I, Świerczek S et al (1997) Polymer blends of natural poly (3-hydroxybutyrate-co-3-hydroxyvalerate) and a synthetic atactic poly (3-hydroxybutyrate). Characterization and biodegradation studies. Macromolecules 30(9):2568–2574. https://doi.org/10.1021/ma961431y

    Article  CAS  Google Scholar 

  25. Gelling I, Tinker A, Rahman HA (1991) Solubility parameters of epoxidised natural rubber.

  26. Ma P, Cai X, Lou X, Dong W, Chen M, Lemstra PJ (2014) Styrene-assisted melt free-radical grafting of maleic anhydride onto poly(β-hydroxybutyrate). Polym Degrad Stab 100:93–100. https://doi.org/10.1016/j.polymdegradstab.2013.12.005

    Article  CAS  Google Scholar 

  27. He JD, Cheung MK, Yu PH, Chen GQ (2001) Thermal analyses of poly (3-hydroxybutyrate), poly (3‐hydroxybutyrate‐co‐3‐hydroxyvalerate), and poly (3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate). J Appl Polym Sci 82(1):90–98. https://doi.org/10.1002/app.1827

    Article  CAS  Google Scholar 

  28. Singh S, Mohanty AK, Sugie T, Takai Y, Hamada H (2008) Renewable resource based biocomposites from natural fiber and polyhydroxybutyrate-co-valerate (PHBV) bioplastic. Compos Part A: Appl Sci Manufac 39(5):875–886. https://doi.org/10.1021/sc500353v

    Article  CAS  Google Scholar 

  29. Yu H-Y, Qin Z-Y, Liu Y-N, Chen L, Liu N, Zhou Z (2012) Simultaneous improvement of mechanical properties and thermal stability of bacterial polyester by cellulose nanocrystals. Carbohydr Polym 89(3):971–978. https://doi.org/10.1016/j.carbpol.2012.04.053

    Article  CAS  PubMed  Google Scholar 

  30. Janigová I, Lacı́k I, Chodák I (2002) Thermal degradation of plasticized poly (3-hydroxybutyrate) investigated by DSC. Polym Degrad Stab 77(1):35–41. https://doi.org/10.1016/S0141-3910(02)00077-0

    Article  Google Scholar 

  31. Pongtanayut K, Thongpin C, Santawitee O (2013) The effect of rubber on morphology, thermal properties and mechanical properties of PLA/NR and PLA/ENR blends. Energy Procedia 34:888–897. https://doi.org/10.1016/j.egypro.2013.06.826

    Article  CAS  Google Scholar 

  32. El-Hadi A, Schnabel R, Straube E, Müller G, Henning S (2002) Correlation between degree of crystallinity, morphology, glass temperature, mechanical properties and biodegradation of poly (3-hydroxyalkanoate) PHAs and their blends. Polym Test 21(6):665–674

    Article  CAS  Google Scholar 

  33. Algaily B, Kaewsakul W, Sarkawi SS, Kalkornsurapranee E (2021) Enabling reprocessability of ENR-based vulcanisates by thermochemically exchangeable ester crosslinks. Plast Rubber Compos 50(7):315–328. https://doi.org/10.1080/14658011.2021.1896093

    Article  CAS  Google Scholar 

  34. Wu H, Tian M, Zhang L, Tian H, Wu Y, Ning N (2014) New understanding of microstructure formation of the rubber phase in thermoplastic vulcanizates (TPV). Soft Matter 10(11):1816–1822. https://doi.org/10.1039/C3SM52375F

    Article  CAS  PubMed  Google Scholar 

  35. Kiruthika A (2022) PHBV based blends and composites. Biodegradable polymers, blends and composites. Elsevier, pp 283–308

  36. Sampath W, Edirisinghe D, Egodage S (2016) Property improvements of natural rubber and low density polyethylene blends through dynamic vulcanization. J Rubber Res Inst Sri Lanka 96:1–11. https://doi.org/10.4038/jrrisl.v96i0.1837

    Article  Google Scholar 

  37. Ramachandran AA, Mathew LP, Thomas S (2019) Effect of MA-g-PP compatibilizer on morphology and electrical properties of MWCNT based blend nanocomposites: New strategy to enhance the dispersion of MWCNTs in immiscible poly (trimethylene terephthalate)/polypropylene blends. Eur Polymer J 118:595–605. https://doi.org/10.1016/j.eurpolymj.2019.06.027

    Article  CAS  Google Scholar 

  38. Liu G-C, He Y-S, Zeng J-B, Xu Y, Wang Y-Z (2014) In situ formed crosslinked polyurethane toughened polylactide. Polym Chem 5(7):2530–2539. https://doi.org/10.1039/C3PY01649H

    Article  CAS  Google Scholar 

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Acknowledgements

We acknowledge the financial support from Thailand Science research and Innovation Fund Chulalongkorn University. Napat Tomano would like to acknowledge the Second Century Fund (C2F), Chulalongkorn university for the support. We also thank the Department of Materials Science, Faculty of Science and Metallurgy and Materials Science Research Institute, Chulalongkorn University for providing the research facilities to make this research possible.

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Authors and Affiliations

  1. Nanoscience and Technology Program, Graduate School, Chulalongkorn University, Bangkok, 10330, Thailand

    Napat Tomano

  2. Polymer Engineering Center, Department of Mechanical Engineering, University of Wisconsin–Madison, Madison, WI, 53706, USA

    Tim A. Osswald

  3. Department of Materials Science, Faculty of Science, Chulalongkorn University, Bangkok, 10330, Thailand

    Pranut Potiyaraj & Orathai Boondamnoen

  4. Metallurgy and Materials Science Research Institute, Chulalongkorn University, Bangkok, 10330, Thailand

    Pranut Potiyaraj & Chuanchom Aumnate

  5. Center of Excellence in Responsive Wearable Materials, Chulalongkorn University, Bangkok, 10330, Thailand

    Pranut Potiyaraj & Chuanchom Aumnate

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  1. Napat Tomano
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Contributions

N.T. performed the experiment, analyzed the data, and wrote the original draft of the main manuscript. T.A.O. and P.P edited the final version of the manuscript. O.B. and C.A designed the research problem and methodology, supervised the project and edited the final version of the manuscript.

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Correspondence to Orathai Boondamnoen.

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Tomano, N., Osswald, T.A., Potiyaraj, P. et al. Toughened Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/Epoxidized Natural Rubber Blends Fabricated by Dynamic Vulcanization and Interfacial Compatibilization. J Polym Environ (2024). https://doi.org/10.1007/s10924-024-03283-9

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