Nowadays, plastic contamination worldwide is a concerning reality that can be addressed with appropriate society education as well as looking for innovative polymeric alternatives based on the reuse of waste and recycling with a circular economy point of view, thus taking into consideration that a future world without plastic is quite impossible to conceive. In this regard, in this review, we focus on sustainable polymeric materials, biodegradable and bio-based polymers, additives, and micro/nanoparticles to be used to obtain new environmentally friendly polymeric-based materials. Although biodegradable polymers possess poorer overall properties than traditional ones, they have gained a huge interest in many industrial sectors due to their inherent biodegradability in natural environments. Therefore, several strategies have been proposed to improve their properties and extend their industrial applications. Blending strategies, as well as the development of composites and nanocomposites, have shown promising perspectives for improving their performances, emphasizing biopolymeric blend formulations and bio-based micro and nanoparticles to produce fully sustainable polymeric-based materials. The Review also summarizes recent developments in polymeric blends, composites, and nanocomposite plasticization, with a particular focus on naturally derived plasticizers and their chemical modifications to increase their compatibility with the polymeric matrices. The current state of the art of the most important bio-based and biodegradable polymers is also reviewed, mainly focusing on their synthesis and processing methods scalable to the industrial sector, such as melt and solution blending approaches like melt-extrusion, injection molding, film forming as well as solution electrospinning, among others, without neglecting their degradation processes.

Polybutylene adipate-co-terephthalate (PBAT) is a biodegradable polymer with good features for packaging applications. However, the mechanical performance and high prices of PBAT limit its current usage at the commercial level. To improve the properties and reduce the cost of PBAT, pine resin derivatives, gum rosin (GR) and pentaerythritol ester of GR (UT), were proposed as sustainable additives. For this purpose, PBAT was blended with 5, 10, and 15 wt.% of additives by melt-extrusion followed by injection moulding. The overall performance of the formulations was assessed by tensile test, microstructural, thermal, and dynamic mechanical thermal analysis. The results showed that although good miscibility of both resins with PBAT matrix was achieved, GR in 10 wt.% showed better interfacial adhesion with the PBAT matrix than UT. The thermal characterization suggested that GR and UT reduce PBAT melting enthalpy and enhance its thermal stability, improving PBAT processability. A 10 wt.% of GR significantly increased the tensile properties of PBAT, while a 15 wt.% of UT maintained PBAT tensile performance. The obtained materials showed higher hydrophobicity than neat PBAT. Thus, GR and UT demonstrated that they are advantageous additives for PBAT–resin compounding for rigid food packaging which are easy to process and adequate for industrial scalability. At the same time, they enhance its mechanical and hydrophobic performance.

Fully bio-based materials based on thermoplastic starch (TPS) were developed starting from corn starch plasticized with glycerol. The obtained TPS was further blended with five pine resin derivatives: gum rosin (GR), disproportionated gum rosin (dehydroabietic acid, RD), maleic anhydride modified gum rosin (CM), pentaerythritol ester of gum rosin (LF), and glycerol ester of gum rosin (UG). The TPS–resin blend formulations were processed by melt extrusion and further by injection moulding to simulate the industrial conditions. The obtained materials were characterized in terms of mechanical, thermal and structural properties. The results showed that all gum rosin-based additives were able to improve the thermal stability of TPS, increasing the degradation onset temperature. The carbonyl groups of gum rosin derivatives were able to interact with the hydroxyl groups of starch and glycerol by means of hydrogen bond interactions producing a significant increase of the glass transition temperature with a consequent stiffening effect, which in turn improve the overall mechanical performance of the TPS-resin injected moulded blends. The developed TPS–resin blends are of interest for rigid packaging applications.

Completely biobased and biodegradable thermoplastic starch (TPS) based materials with a tunable performance were prepared for food packaging applications. Five blends were prepared by blending TPS with 10 wt%. of different pine resins derivatives: gum rosin (GR), disproportionated gum rosin (RD), maleic anhydride-modified gum rosin (CM), pentaerythritol ester of gum rosin (LF), and glycerol ester of gum rosin (UG). The materials were characterized in terms of thermo-mechanical behavior, surface wettability, color performance, water absorption, X-ray diffraction pattern, and disintegration under composting conditions. It was determined that pine resin derivatives increase the hydrophobicity of TPS and also increase the elastic component of TPS which stiffen the TPS structure. The water uptake study revealed that GR and LF were able to decrease the water absorption of TPS, while the rest of the resins kept the water uptake ability. X-ray diffraction analyses revealed that GR, CM, and RD restrain the aging of TPS after 24 months of aging. Finally, all TPS-resin blends were disintegrated under composting conditions during the thermophilic incubation period (90 days). Because of the TPS-resin blend’s performance, the prepared materials are suitable for biodegradable rigid food packaging applications.

In this work, different materials for three-dimensional (3D)-printing were studied, which based on polycaprolactone with two natural additives, gum rosin, and beeswax. During the 3D-printing process, the bed and extrusion temperatures of each formulation were established. After, the obtained materials were characterized by mechanical, thermal, and structural properties. The results showed that the formulation with containing polycaprolactone with a mixture of gum rosin and beeswax as additive behaved better during the 3D-printing process. Moreover, the miscibility and compatibility between the additives and the matrix were concluded through the thermal assessment. The mechanical characterization established that the addition of the mixture of gum rosin and beeswax provides greater tensile strength than those additives separately, facilitating 3D-printing. In contrast, the addition of beeswax increased the ductility of the material, which makes the 3D-printing processing difficult. Despite the fact that both natural additives had a plasticizing effect, the formulations containing gum rosin showed greater elongation at break. Finally, Fourier-Transform Infrared Spectroscopy assessment deduced that polycaprolactone interacts with the functional groups of the additives.