Evaluation of the activity of natural phenolic antioxidants, extracted from industrial coffee residues, on the stability of poly(1,4‐butylene succinate) formulations

In this work, the evaluation of the antioxidant activity of natural phenolic compounds is performed and compared to that of a conventional antioxidative agent. Phenolic molecules, extracted from industrial processing coffee residues, are added to a matrix of poly(1,4-butylene succinate) (PBS). The apparent activation energy (Ea) of the thermo-oxidative degradation is calculated by employing different methods like Kissinger-Akahira-Sunose, Flynn-Wall-Ozawa and Friedman. The results are compared with the antioxidant activity evaluation obtained through the ABTS radical scavenging assay. From the average activation energies, it is observed that the addition of the natural antioxidants led to an increase in the activation energy of the degradation process as a function of the phenolic compound content. This trend is confirmed by the results of the ABTS assay. Hence, this study proves that the active molecules extracted from agri-food waste could be employed to improve the antioxidant capacity of the biopolymer, even if the composition of the extract must be evaluated in order to mitigate the effects of other components

From winery waste to bioactive compounds and new polymeric biocomposites: a contribution to the circular economy concept

The paper aims at optimising and validating possible routes toward the full valorisation of grape agrowaste to produce bioactive molecules and new materials. Starting from Merlot red pomace, phenol complex mixtures were successfully extracted by using two different approaches. Extracts obtained by solvent-based (SE) technique contained up to 46.9 gGAeq/kgDW of total phenols. Depending on the used solvent, the prevalence of compounds belonging to different phenol families was achieved. Pressurized liquid extraction (PLE) gave higher total phenol yields (up to 79 gGAeq/kgDW) but a lower range of extracted compounds. All liquid extracts exerted strong antioxidant properties. Moreover, both SE and PLE extraction solid residues were directly exploited (between 5 and 20% w/w) to prepare biocomposite materials by direct mixing via an eco-friendly approach with PHBV polymer. The final composites showed mechanical characteristics similar to PHVB matrix. The use of pomace residues in biocomposites could therefore bring both to the reduction of the cost of the final material, as a lower amount of costly PHBV is used. The present research demonstrated the full valorisation of grape pomace, an agrowaste produced every year in large amounts and having a significant environmental impact

Polymer design: tailoring the materials properties according to the industrial demands

The industry requests are various and usually driven by several factors, like environmental sustainability, product and process costs, market availability of reactants, and consumers perception. From time to time, Industry addresses to Academia different questions relating to the possibility to improve product performances, decrease environmental impact, limit production costs, and optimize material recycling. In order to tackle such a range of issues, the deep investigation on polymeric chemical structures as well as structure-property relationships allow to design a priori the materials able to satisfy the industrial needs. As examples, in order to enlarge the applications of barrier polymers, water solubility can be imparted to the poly(hexamethylene isophthalamide) by introducing a low amount of sulfonated groups along the macromolecular chains. The macromolecular rigidity of poly(m-xylylene adipamide) can be modulated by using monomers bearing asymmetric aromatic rings or short aliphatic chains. Otherwise, the gas barrier properties of poly(propylene 2,5- furandicarboxylate) can be notably increased by controlling the crystallization process. On the other hand, the end-used poly(ethylene terephthalate) and bisphenol A polycarbonate can be conveniently recycled and exploited in powder coating applications through its depolymerization/repolymerization with suitable monomers

New biomaterials for packaging: a green approach to biopolymers and biocomposites

The impellent global environmental issues related to plastic materials can be addressed by following two different approaches: i) the development of synthetic strategies towards novel bio-based polymers, deriving from biomasses and thus identifiable as CO2-neutral materials, and ii) the development of new plastic materials, such as biocomposites, which are bio-based and biodegradable and therefore able to counteract the accumulation of plastic waste. In this framework, this dissertation presents extensive research efforts have been devoted to the synthesis and characterization of polyesters based on various bio-based monomers, including ω-pentadecalactone, vanillic acid, 2,5-furan dicarboxylic acid, and 5-hydroxymethylfurfural. With the aim of achieving high molecular weight polyesters, different synthetic strategies have been used as melt polycondensation, enzymatic polymerization, ring-opening polymerization and chain extension reaction. In particular, poly(ethylene vanillate) (PEV), poly(ω-pentadecalactone) (PPDL), poly(ethylene vanillate-co-pentadecalactone) (P(EV-co-PDL)), poly(2-hydroxymethyl 5-furancarboxylate) (PHMF), poly(ethylene 2,5-furandicarboxylate) (PEF) with different amount of diethylene glycol (DEG) unit amount, poly(propylene 2,5-furandicarboxylate) (PPF), poly(hexamethylene 2,5-furandicarboxylate), (PHF) have been prepared and extensively characterized. To improve the lacks of poly(hydroxybutyrate-co-valerate) (PHBV), its minimal formulations with natural additives and its blending with medium chain length PHAs (mcl-PHAs) have been tested. Additionally, this dissertation presents new biocomposites based on polylactic acid (PLA), poly(butylene succinate) (PBS), and PHBV, which are polymers both bio-based and biodegradable. To maintain their biodegradability only bio-fillers have been taken into account as reinforcing agents. Moreover, the commitment to sustainability has further limited the selection and led to the exclusive use of agricultural waste as fillers. Detailly, biocomposites have been obtained and discussed by using the following materials: PLA and agro-wastes like tree pruning, potato peels, and hay leftovers; PBS and exhausted non-compliant coffee green beans; PHBV and industrial starch extraction residues