Journal of Polymers and the Environment

, Volume 28, Issue 3, pp 1050–1067 | Cite as

Green Biodegradable Thermoplastic Natural Rubber Based on Epoxidized Natural Rubber and Poly(butylene succinate) Blends: Influence of Blend Proportions

  • Parisa Faibunchan
  • Skulrat PichaiyutEmail author
  • Claudia Kummerlöwe
  • Norbert Vennemann
  • Charoen NakasonEmail author
Original Paper


Green biodegradable thermoplastic natural rubber based on epoxidized natural rubber (ENR) and poly(butylene succinate) (PBS) blends was prepared via simple blend (SB) or via dynamic vulcanization (DV). Influence of blend proportions of ENR and PBS on morphological, dynamic, mechanical, dynamic mechanical, thermal properties, and water absorption together with biodegradability were investigated. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were also used to assess phase morphologies in the ENR/PBS blends. It was found that the ENR/PBS simple blend had co-continuous phase structure, while the dynamically cured ENR/PBS blend (DV) has spherical micron-sized crosslinked ENR particles dispersed in the PBS matrix. In addition, the particle size of vulcanized ENR domains of DV and the grain size of ENR and PBS phases in the simple blend decreased with increasing PBS content up to 50 wt%. This might be caused by interfacial adhesion effects between the phases. However, increasing the ENR fraction to 70 wt% caused increasing of elasticity in terms of shear viscosity, shear modulus, storage modulus, together with elongation at break, and tension set. It was also found that mechanical and thermal properties as well as biodegradability of dynamically cured ENR/PBS blends were better than for the simple blend counterparts, That is, the lowest biodegradability, as indicated by the least weight loss, is seen for the 50/50 ENR-25/PBS simple blend (about 1.2%) and dynamic vulcanizate (about 0.6%).


Epoxidized natural rubber (ENR) Poly(butylene succinate) Biodegradability Water absorption Dynamic vulcanization (DV) 



The authors acknowledge financial support by the Thailand Research Fund (TRF) through the Royal Golden Jubilee Ph.D. Program (Grant No. PHD/0208/2557) to Associate Professor Dr. Charoen Nakason as a principal researcher, and to Miss Parisa Faibunchan as the research assistant, and from the Graduate School, Prince of Songkla University. The authors would like to express their gratitude to Faculty of Engineering and Computer Science, University of Applied Sciences Osnabrück, Germany, which is gratefully acknowledged for providing access to its facilities and also to Dr. Seppo Karrila for English proof of a manuscript.


  1. 1.
    Vroman I, Tighzert L (2009) Biodegradable polymers. Materials 2:307–344CrossRefGoogle Scholar
  2. 2.
    Cuq B, Gontard N, Guilbert S (1998) Proteins as agricultural polymers for packaging production. Cereal Chem 75:1–9CrossRefGoogle Scholar
  3. 3.
    Guilbert S, Gontard N (2005) Agro-polymers for edible and biodegradable films: review of agricultural polymeric materials, physical and mechanical characteristics, in Innovations in food packaging. Elsevier, pp 263–276.Google Scholar
  4. 4.
    Zhang K, Mohanty AK, Misra M (2012) Fully biodegradable and biorenewable ternary blends from polylactide, poly (3-hydroxybutyrate-co-hydroxyvalerate) and poly (butylene succinate) with balanced properties. ACS Appl Mater Interfaces 4:3091–3101CrossRefPubMedPubMedCentralGoogle Scholar
  5. 5.
    Pillon L, Utracki L (1984) Compatibilization of polyester/polyamide blends via catalytic ester-amide interchange reaction. Polym Eng Sci 24:1300–1305CrossRefGoogle Scholar
  6. 6.
    Lu D, Xiao C, Xu S (2009) Starch-based completely biodegradable polymer materials. Express Polym Lett 3:366–375Google Scholar
  7. 7.
    Mani R, Bhattacharya M (2001) Properties of injection moulded blends of starch and modified biodegradable polyesters. Eur Polym J 37:515–526CrossRefGoogle Scholar
  8. 8.
    Sionkowska A (2011) Current research on the blends of natural and synthetic polymers as new biomaterials. Prog Polym Sci 36:1254–1276CrossRefGoogle Scholar
  9. 9.
    Gilmore DF, Antoun S, Lenz RW (1993) Fuller RC (2002) Degradation of poly (β-hydroxyalkanoates) and polyolefin blends in a municipal wastewater treatment facility. J Environ Polym Degrad 1:269–274CrossRefGoogle Scholar
  10. 10.
    Biresaw G, Carriere C (2002) Interfacial tension of poly (lactic acid)/polystyrene blends. J Polym Sci Pol Phys 40:2248–2258CrossRefGoogle Scholar
  11. 11.
    Sarazin P, Favis BD (2005) Influence of temperature-induced coalescence effects on co-continuous morphology in poly (ε-caprolactone)/polystyrene blends. Polymer 46:5966–5978CrossRefGoogle Scholar
  12. 12.
    Huneault MA, Li H (2007) Morphology and properties of compatibilized polylactide/thermoplastic starch blends. Polymer 48:270–280CrossRefGoogle Scholar
  13. 13.
    Marin E, Briceño MI, Caballero-George C (2013) Critical evaluation of biodegradable polymers used in nanodrugs. Int J Nanomed 8:3071Google Scholar
  14. 14.
    Petersen K, Nielsen PV, Bertelsen G, Lawther M, Olsen MB, Nilsson NH, Mortensen G (1999) Potential of biobased materials for food packaging. Trends Food Sci Technol 10:52–68CrossRefGoogle Scholar
  15. 15.
    Nair LS, Laurencin CT (2007) Biodegradable polymers as biomaterials. Prog Polym Sci 32:762–798CrossRefGoogle Scholar
  16. 16.
    Bode HB, Kerkhoff K, Jendrossek D (2001) Bacterial degradation of natural and synthetic rubber. Biomacromol 2:295–303CrossRefGoogle Scholar
  17. 17.
    Bitinis N, Verdejo R, Cassagnau P, Lopez-Manchado M (2011) Structure and properties of polylactide/natural rubber blends. Mater Chem Phys 129:823–831CrossRefGoogle Scholar
  18. 18.
    Kuntanoo K, Promkotra S, Kaewkannetra P (2013) Biodegradation of polyhydroxybutyrate-co-hydroxyvalerate (PHBV) blended with natural rubber in soil environment. Int Sci Index 7:12Google Scholar
  19. 19.
    Coelho JF, Góis JR, Fonseca AC, Gil M (2010) Modification of poly (3-hydroxybutyrate)-co-poly (3-hydroxyvalerate) with natural rubber, Journal of applied polymer science. J Appl Polym Sci 116:718–726Google Scholar
  20. 20.
    Kaewkannetra P, Promkotra S (2013) Quality improvement and characteristics of polyhydroxyalkanoates (PHAs) and natural latex rubber blends, in Defect and Diffusion Forum. Trans Tech Publications, pp 49–54.Google Scholar
  21. 21.
    Cheong KS, Balasubramaniam J-R, Hung YP, Chuong WS, Amartalingam R (2010) Development of biodegradable plastic composite blends based on sago derived starch and natural rubber. Pertanika J Sci Technol 18:411–420Google Scholar
  22. 22.
    Pichaiyut S, Wisunthorn S, Thongpet C, Nakason C (2016) Novel ternary blends of natural rubber/linear low-density polyethylene/thermoplastic starch: influence of epoxide level of epoxidized natural rubber on blend properties. Iran Polym J 25:711–723CrossRefGoogle Scholar
  23. 23.
    Kahar A, Ismail H, Othman N (2012) Effects of polyethylene-grafted maleic anhydride as a compatibilizer on the morphology and tensile properties of (thermoplastic tapioca starch)/(high-density polyethylene)/(natural rubber) blends. J Vinyl Addit Technol 18:65–70CrossRefGoogle Scholar
  24. 24.
    Carvalho A, Job A, Alves N, Curvelo A, Gandini A (2003) Thermoplastic starch/natural rubber blends. Carbohyd Polym 53:95–99CrossRefGoogle Scholar
  25. 25.
    Jaratrotkamjorn R, Khaokong C, Tanrattanakul V (2012) Toughness enhancement of poly (lactic acid) by melt blending with natural rubber. J Appl Polym Sci 124:5027–5036Google Scholar
  26. 26.
    Suksut B, Deeprasertkul C (2011) Effect of nucleating agents on physical properties of poly (lactic acid) and its blend with natural rubber. J Polym Environ 19:288–296CrossRefGoogle Scholar
  27. 27.
    Ayutthaya WDN, Poompradub S (2014) Thermal and mechanical properties of poly (lactic acid)/natural rubber blend using epoxidized natural rubber and poly (methyl methacrylate) as co-compatibilizers. Macromol Res 22:686–692CrossRefGoogle Scholar
  28. 28.
    Yoksan R (2008) Epoxidized natural rubber for adhesive applications. Kasetsart J (Natural Science) 42:325–332Google Scholar
  29. 29.
    Chutamas M, Jackapon S, Hyun JK, Klanarong S (2014) Improving mechanical properties of poly-β-hydroxybutyrate-co-β-hydroxyvalerate by blending with natural rubber and epoxidized natural rubber, in Advanced Materials Research. Trans Tech Publications, pp 179–182.Google Scholar
  30. 30.
    Maneewong C, Sunthornvarabhas J, Kim H, Sriroth K (2014) Improving mechanical properties of poly-ß-hydroxybutyrate-co-ß-hydroxyvalerate by blending with natural rubber and epoxidized natural rubber. Adv Mat Res 983:179–182Google Scholar
  31. 31.
    Jantanasakulwong K, Leksawasdi N, Seesuriyachan P, Wongsuriyasak S, Techapun C, Ougizawa T (2016) Reactive blending of thermoplastic starch, epoxidized natural rubber and chitosan. Eur Polym J 84:292–299CrossRefGoogle Scholar
  32. 32.
    Yew G, Chow W, Mohd Ishak Z, Mohd Yusof A (2009) Natural weathering of poly (lactic acid): effects of rice starch and epoxidized natural rubber. J Elastom Plast 41:369–382CrossRefGoogle Scholar
  33. 33.
    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 Proced 34:888–897CrossRefGoogle Scholar
  34. 34.
    Lee S-H, Wang S (2006) Biodegradable polymers/bamboo fiber biocomposite with bio-based coupling agent. Composites A 37:80–91CrossRefGoogle Scholar
  35. 35.
    Pichaiyut S, Nakason C, Kummerlöwe C, Vennemann N (2012) Thermoplastic elastomer based on epoxidized natural rubber/thermoplastic polyurethane blends: influence of blending technique. Polym Adv Technol 23:1011–1019CrossRefGoogle Scholar
  36. 36.
    Nakason C, Worlee A, Salaeh S (2008) Effect of vulcanization systems on properties and recyclability of dynamically cured epoxidized natural rubber/polypropylene blends. Polym Test 27:858–869CrossRefGoogle Scholar
  37. 37.
    Narathichat M, Kummerlöwe C, Vennemann N, Nakason C (2011) Thermoplastic natural rubber based on polyamide-12: Influence of blending technique and type of rubber on temperature scanning stress relaxation and other related properties. J Appl Polym Sci 121:805–814CrossRefGoogle Scholar
  38. 38.
    Tham WL, Poh BT, Mohd Ishak ZA, Chow WS (2016) Epoxidized natural rubber toughened poly (lactic acid)/halloysite nanocomposites with high activation energy of water diffusion. J Appl Polym Sci. CrossRefGoogle Scholar
  39. 39.
    Wahit MU, Hassan A, Ibrahim AN, Zawawi NA, Kunasegeran K (2015) Mechanical, thermal and chemical resistance of epoxidized natural rubber toughened polylactic acid blends. Sains Malays 44:1615–1623Google Scholar
  40. 40.
    Zeng J-B, Jiao L, Li Y-D, Srinivasan M, Li T, Wang Y-Z (2011) Bio-based blends of starch and poly (butylene succinate) with improved miscibility, mechanical properties, and reduced water absorption. Carbohyd Polym 83:762–768CrossRefGoogle Scholar
  41. 41.
    Riyajan S-A, Sasithornsonti Y, Phinyocheep P (2012) Green natural rubber-g-modified starch for controlling urea release. Carbohyd Polym 89:251–258CrossRefGoogle Scholar
  42. 42.
    Faibunchan P, Nakaramontri Y, Chueangchayaphan W, Pichaiyut S, Kummerlöwe C, Vennemann N, Nakason C (2018) Novel biodegradable thermoplastic elastomer based on poly (butylene succinate) and epoxidized natural rubber simple blends. J Polym Environ 26:2867–2880CrossRefGoogle Scholar
  43. 43.
    Steinmann S, Gronski W, Friedrich C (2001) Cocontinuous polymer blends: influence of viscosity and elasticity ratios of the constituent polymers on phase inversion. Polymer 42:6619–6629CrossRefGoogle Scholar
  44. 44.
    Gergen W, Lutz R and Davison S (1996) Hydrogenated block copolymers in thermoplastic elastomer interpenetrating polymer networks. Thermoplast Elastom.Google Scholar
  45. 45.
    Utracki L (1991) On the viscosity-concentration dependence of immiscible polymer blends. J Rheol 35:1615–1637CrossRefGoogle Scholar
  46. 46.
    Yuan D, Xu C, Chen Z, Chen Y (2014) Crosslinked bicontinuous biobased polylactide/natural rubber materials: super toughness, “net-like”-structure of NR phase and excellent interfacial adhesion. Polym Test 38:73–80CrossRefGoogle Scholar
  47. 47.
    Faibunchan P, Pichaiyut S, Chueangchayaphan W, Kummerlöwe C, Venneman N, Nakason C (2019) Influence type of natural rubber on properties of green biodegradable thermoplastic natural rubber based on poly (butylene succinate). Polym Adv Technol 30(4):1010–1026CrossRefGoogle Scholar
  48. 48.
    Mathew AP, Packirisamy S, Thomas S (2001) Studies on the thermal stability of natural rubber/polystyrene interpenetrating polymer networks: thermogravimetric analysis. Polym Degrad Stabil 72:423–439CrossRefGoogle Scholar
  49. 49.
    Noriman NZ, Ismail H (2012) Effect of epoxidized natural rubber on thermal properties, fatigue life, and natural weathering test of styrene butadiene rubber/recycled acrylonitrile-butadiene rubber (SBR/NBRr) blends. J Appl Polym Sci 123:779–787CrossRefGoogle Scholar
  50. 50.
    Thongpin C, Kuttanate N, Kampuang K, Suwanwanit N (2012) Study of dynamic vulcanized PLA/ENR TPV filled with various organic modified MMT (OMMT. Jom-J Min Met Mat S 22.Google Scholar
  51. 51.
    Liu X, Khor S, Petinakis E, Yu L, Simon G, Dean K, Bateman S (2010) Effects of hydrophilic fillers on the thermal degradation of poly (lactic acid). Thermochim Acta 509:147–151CrossRefGoogle Scholar
  52. 52.
    Nun-anan P, Wisunthorn S, Pichaiyut S, Vennemann N, Nakason C (2018) Novel approach to determine non-rubber content in Hevea brasiliensis: Influence of clone variation on properties of un-vulcanized natural rubber. Ind Crop Prod 118:38–47CrossRefGoogle Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2020

Authors and Affiliations

  1. 1.Department of Rubber Technology, Faculty of Science and Industrial TechnologyPrince of Songkla UniversitySurat ThaniThailand
  2. 2.Faculty of Engineering and Computer ScienceUniversity of Applied Sciences OsnabrückOsnabrückGermany

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