In Service Performance of Toughened PHBV/TPU Blends Obtained by Reactive Extrusion for Injected Parts

Moving toward a more sustainable production model based on a circular economy, biopolymers are considered as one of the most promising alternatives to reduce the dependence on oil-based plastics. Polyhydroxybutyrate-co-valerate (PHBV), a bacterial biopolyester from the polyhydroxialkanoates (PHAs) family, seems to be an attractive candidate to replace commodities in many applications such as rigid packaging, among others, due to its excellent overall physicochemical and mechanical properties. However, it presents a relatively poor thermal stability, low toughness and ductility, thus limiting its applicability with respect to other polymers such as polypropylene (PP). To improve the performance of PHBV, reactive blending with an elastomer seems to be a proper cost-effective strategy that would lead to increased ductility and toughness by rubber toughening mechanisms. Hence, the objective of this work was the development and characterization of toughness-improved blends of PHBV with thermoplastic polyurethane (TPU) using hexamethylene diisocyanate (HMDI) as a reactive extrusion agent. To better understand the role of the elastomer and the compatibilizer, the morphological, rheological, thermal, and mechanical behavior of the blends were investigated. To explore the in-service performance of the blends, mechanical and long-term creep characterization were conducted at three different temperatures (−20, 23, 50 °C). Furthermore, the biodegradability in composting conditions has also been tested. The results showed that HMDI proved its efficiency as a compatibilizer in this system, reducing the average particle size of the TPU disperse phase and enhancing the adhesion between the PHBV matrix and TPU elastomer. Although the sole incorporation of the TPU leads to slight improvements in toughness, the compatibilizer plays a key role in improving the overall performance of the blends, leading to a clear improvement in toughness and long-term behavior.

[1]  F. Adani,et al.  The role of waste management in reducing bioplastics' leakage into the environment: A review. , 2021, Bioresource technology.

[2]  P. Cinelli,et al.  Immiscible PHB/PB S and PHB/PBSA blends: morphology, phase composition and modelling of elastic modulus , 2021, Polymer International.

[3]  I. Fekete,et al.  Highly toughened blends of poly(lactic acid) (PLA) and natural rubber (NR) for FDM-based 3D printing applications: The effect of composition and infill pattern , 2021, Polymer Testing.

[4]  M. Reis,et al.  Microbial production of medium-chain length polyhydroxyalkanoates , 2021 .

[5]  Alper Kasgoz Mechanical, Tensile Creep and Viscoelastic Properties of Thermoplastic Polyurethane/Polycarbonate Blends , 2021, Fibers and Polymers.

[6]  S. Torres‐Giner,et al.  Emerging Trends in Biopolymers for Food Packaging , 2021 .

[7]  M. Hussein,et al.  Properties and Applications of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Biocomposites , 2020, Journal of Polymers and the Environment.

[8]  S. Torres‐Giner,et al.  Environmentally Friendly Polymers and Polymer Composites , 2020, Materials.

[9]  Reena Gupta,et al.  Polyhydroxyalkanoate (PHA): Properties and Modifications , 2020 .

[10]  M. Kontopoulou,et al.  Advances in peroxide‐initiated graft modification of thermoplastic biopolyesters by reactive extrusion , 2020, The Canadian Journal of Chemical Engineering.

[11]  M. Misra,et al.  Review of recent advances in the biodegradability of polyhydroxyalkanoate (PHA) bioplastics and their composites , 2020, Green Chemistry.

[12]  D. Rodrigue,et al.  Compatibilization of PA6/ABS blend by SEBS-g-MA: morphological, mechanical, thermal, and rheological properties , 2020, The International Journal of Advanced Manufacturing Technology.

[13]  Leyi Chen,et al.  Enhancing toughness of poly (lactic acid)/Thermoplastic polyurethane blends via increasing interface compatibility by polyurethane elastomer prepolymer and its toughening mechanism , 2020 .

[14]  M. Misra,et al.  Toughening of Biodegradable Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/Poly(ε-caprolactone) Blends by In Situ Reactive Compatibilization , 2020, ACS omega.

[15]  Lei Jiang,et al.  Advances in toughened polymer materials by structured rubber particles , 2019, Progress in Polymer Science.

[16]  J. Rabolt,et al.  Microstructure effects on the rheology of nanoclay‐filled PHB/LDPE blends , 2019, Polymer Composites.

[17]  K. Cornish,et al.  Optimal mechanical properties of biodegradable natural rubber-toughened PHBV bioplastics intended for food packaging applications , 2019, Food Packaging and Shelf Life.

[18]  A. Frache,et al.  PLA/PHB Blends: Biocompatibilizer Effects , 2019, Polymers.

[19]  K. Cornish,et al.  Synergistic Mechanisms Underlie the Peroxide and Coagent Improvement of Natural-Rubber-Toughened Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Mechanical Performance , 2019, Polymers.

[20]  P. Ma,et al.  Design of Supertoughened and Heat-Resistant PLLA/Elastomer Blends by Controlling the Distribution of Stereocomplex Crystallites and the Morphology , 2019, Macromolecules.

[21]  J. Anakabe,et al.  PHBV/TPU/cellulose compounds for compostable injection molded parts with improved thermal and mechanical performance , 2018, Journal of Applied Polymer Science.

[22]  L. Cabedo,et al.  Toughness Enhancement of PHBV/TPU/Cellulose Compounds with Reactive Additives for Compostable Injected Parts in Industrial Applications , 2018, International journal of molecular sciences.

[23]  L. Cabedo,et al.  Biocomposites of different lignocellulosic wastes for sustainable food packaging applications , 2018, Composites Part B: Engineering.

[24]  W. Punyodom,et al.  Biodegradable Compatibilized Poly(l-lactide)/Thermoplastic Polyurethane Blends: Design, Preparation and Property Testing , 2018, Journal of Polymers and the Environment.

[25]  A. Haghtalab,et al.  Rheology and morphology study of immiscible linear low‐density polyethylene/poly(lactic acid) blends filled with nanosilica particles , 2017 .

[26]  M. Bechelany,et al.  Potential of polyhydroxyalkanoate (PHA) polymers family as substitutes of petroleum based polymers for packaging applications and solutions brought by their composites to form barrier materials , 2017 .

[27]  Zibiao Li,et al.  Recent advances in the development of biodegradable PHB-based toughening materials: Approaches, advantages and applications. , 2017, Materials science & engineering. C, Materials for biological applications.

[28]  Maria A M Reis,et al.  Recent Advances and Challenges towards Sustainable Polyhydroxyalkanoate (PHA) Production , 2017, Bioengineering.

[29]  L. Cabedo,et al.  Compatibilization of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)–poly(lactic acid) blends with diisocyanates , 2017 .

[30]  L. Cabedo,et al.  Biodegradable poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/thermoplastic polyurethane blends with improved mechanical and barrier performance , 2016 .

[31]  J. Covas,et al.  Film blowing of PHBV blends and PHBV-based multilayers for the production of biodegradable packages , 2016 .

[32]  V. Guillard,et al.  Vegetal fiber‐based biocomposites: Which stakes for food packaging applications? , 2016 .

[33]  S. Mohanty,et al.  Mechanism of Toughening in Rubber Toughened Polyolefin—A Review , 2015 .

[34]  M. Kaseem,et al.  Biodegradable polymer blends and composites: An overview , 2014, Polymer Science Series A.

[35]  Y. Grohens,et al.  Synergistic effect of compatibilizer and cloisite 30B on the functional properties of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/polylactide blends , 2014 .

[36]  M. Koller Poly(hydroxyalkanoates) for Food Packaging: Application and Attempts towards Implementation , 2014 .

[37]  Kunyu Zhang,et al.  Toughened Sustainable Green Composites from Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Based Ternary Blends and Miscanthus Biofiber , 2014 .

[38]  Lisheng Zhang,et al.  Improvement in toughness of polylactide by melt blending with bio-based poly(ester)urethane , 2014, Chinese Journal of Polymer Science.

[39]  Michael Niaounakis,et al.  Thermomechanical properties and rheological behavior of biodegradable composites , 2013 .

[40]  C. Bucknall,et al.  Notched impact behaviour of polymer blends: Part 2: Dependence of critical particle size on rubber particle volume fraction , 2013 .

[41]  P. J. Lemstra,et al.  Toughening of PHBV/PBS and PHB/PBS Blends via In situ Compatibilization Using Dicumyl Peroxide as a Free‐Radical Grafting Initiator , 2012 .

[42]  Pierre J. Carreau,et al.  Control of thermal degradation of polylactide (PLA)-clay nanocomposites using chain extenders , 2012 .

[43]  P. Carreau,et al.  Polylactide (PLA)-clay nanocomposites prepared by melt compounding in the presence of a chain extender , 2012 .

[44]  C. Bucknall,et al.  Notched impact behavior of polymer blends: Part 1: New model for particle size dependence , 2009 .

[45]  Valentina Siracusa,et al.  Biodegradable polymers for food packaging: a review , 2008 .

[46]  M. Todo,et al.  Improvement of impact fracture properties of PLA/PCL polymer blend due to LTI addition , 2006 .

[47]  Jagjit Singh,et al.  Evaluation of oriented poly(lactide) polymers vs. existing PET and oriented PS for fresh food service containers , 2005 .

[48]  F. Kopinke,et al.  Mechanistic aspects of the thermal degradation of poly(lactic acid) and poly(β-hydroxybutyric acid) , 1997 .

[49]  A. Argon,et al.  Toughening mechanism of rubber-modified polyamides , 1995 .

[50]  G. Groeninckx,et al.  Toughening behaviour of rubber-modified thermoplastic polymers involving very small rubber particles: 1. A criterion for internal rubber cavitation , 1994 .

[51]  G. Impallomeni,et al.  Thermal degradation of microbial poly(4-hydroxybutyrate) , 1994 .

[52]  Souheng Wu Phase structure and adhesion in polymer blends: a criterion for rubber toughening , 1985 .

[53]  P. Barham,et al.  Crystallization and morphology of a bacterial thermoplastic: poly-3-hydroxybutyrate , 1984 .

[54]  M. A. Ghalia,et al.  Biobased Thermoplastic Polyurethanes and Their Capability to Biodegradation , 2021 .

[55]  H. Wiesmeth Plastics in a circular economy , 2021, Implementing the Circular Economy for Sustainable Development.

[56]  J. Menczel Dynamic mechanical analysis (DMA) in fiber research , 2020 .

[57]  S Mehdi Emadian,et al.  Biodegradation of bioplastics in natural environments. , 2017, Waste management.

[58]  A. Patil,et al.  An overview of Polymeric Materials for Automotive Applications , 2017 .

[59]  H. Voorwald,et al.  Vegetal fibers in polymeric composites: a review , 2015 .

[60]  A. K. Matta,et al.  Preparation and Characterization of Biodegradable PLA/PCL Polymeric Blends , 2014 .

[61]  Andrea Lazzeri,et al.  Polyhydroxyalkanoate (PHA): Review of synthesis, characteristics, processing and potential applications in packaging , 2014 .

[62]  O. Santawitee,et al.  The Effect of Rubber on Morphology, Thermal Properties and Mechanical Properties of PLA/NR and PLA/ENR Blends☆ , 2013 .

[63]  Meifang Zhu,et al.  Reducing the formation of six-membered ring ester during thermal degradation of biodegradable PHBV to enhance its thermal stability , 2009 .

[64]  COMMUNICATION FROM THE COMMISSION TO THE EUROPEAN PARLIAMENT, THE COUNCIL, THE EUROPEAN ECONOMIC AND SOCIAL COMMITTEE AND THE COMMITTEE OF THE REGIONS , 2016 .

[65]  D. Paulb,et al.  Notched impact behavior of polymer blends : Part 1 : New model for particle size dependence , 2022 .