VIII INTERNATIONAL CONFERENCE ON “TIMES OF POLYMERS AND COMPOSITES”: From Aerospace to Nanotechnology, 2016
The Diels–Alder reaction between furan and maleimide moieties is a well-known and widely used str... more The Diels–Alder reaction between furan and maleimide moieties is a well-known and widely used strategy to build bio-based macromolecular structures with peculiar properties. The furan-maleimide adducts are thermally reversible because they can be broken above about 120°C and recombined at lower temperatures. At the moment only the monomers exhibiting the furan or the maleimide moieties on their extremity are used in order to get linear or cross-linked polymeric structures. The innovative idea described here consists in using a monomer bearing two carboxylic acidic groups on its extremities and a furan-maleimide Diels-Alder adduct within its structure. This monomer can give rise to classical polycondensation reactions leading to polymers. These polymers (which are polyesters in the present case) can be broken at high temperatures in correspondence of the furane-maleimide Diels-Alder adduct leading to segments exhibiting furan or maleimide moieties at their extremities, which at lower temperature recombine ...
The depletion of fossil resources and the growing demand for plastic waste reduction has put indu... more The depletion of fossil resources and the growing demand for plastic waste reduction has put industries and academic researchers under pressure to develop increasingly sustainable packaging solutions that are both functional and circularly designed. In this review, we provide an overview of the fundamentals and recent advances in biobased packaging materials, including new materials and techniques for their modification as well as their end-of-life scenarios. We also discuss the composition and modification of biobased films and multilayer structures, with particular attention to readily available drop-in solutions, as well as coating techniques. Moreover, we discuss end-of-life factors, including sorting systems, detection methods, composting options, and recycling and upcycling possibilities. Finally, regulatory aspects are pointed out for each application scenario and end-of-life option. Moreover, we discuss the human factor in terms of consumer perception and acceptance of upcyc...
The use of bioplastic mulch in agriculture has increased dramatically in the last years throughou... more The use of bioplastic mulch in agriculture has increased dramatically in the last years throughout the world. Nowadays, biodegradable materials for mulching films strive to constitute a reliable and more sustainable alternative to classical materials such as polyethylene (PE). The main challenge is to improve their durability in the soil to meet the required service length for crop farming by using benign and sustainable antioxidant systems. Here, we report the design and fabrication of biodegradable materials based on polybutylene (succinate adipate) (PBSA) for mulching applications, incorporating a fully biobased polymeric antioxidant deriving from ferulic acid, which can be extracted from an industrial by-product. Poly-dihydro (ethylene ferulate) (PHEF) from ferulic acid was synthesized by a two-step polymerization process. It is characterized by improved thermal stability in comparison with ferulic acid monomer and therefore suitable for common industrial processing conditions. ...
2,5‐Furandicarboxylic acid (FDCA) is currently considered one of the most relevant bio‐sourced bu... more 2,5‐Furandicarboxylic acid (FDCA) is currently considered one of the most relevant bio‐sourced building blocks, representing a fully sustainable competitor for terephthalic acid as well as the main component in green polymers such as poly(ethylene 2,5‐furandicarboxylate) (PEF). The oxidation of biobased 5‐hydroxymethylfurfural (HMF) represents the most straightforward approach to obtain FDCA, thus attracting the attention of both academia and industries, as testified by Avantium with the creation of a new plant expected to produce 5000 tons per year. Several approaches allow the oxidation of HMF to FDCA. Metal‐mediated homogeneous and heterogeneous catalysis, metal‐free catalysis, electrochemical approaches, light‐mediated procedures, as well as biocatalytic processes share the target to achieve FDCA in high yield and mild conditions. This Review aims to give an up‐to‐date overview of the current developments in the main synthetic pathways to obtain FDCA from HMF, with a specific fo...
Urban waste can be valorized within a biorefinery approach, producing platform chemicals, biopoly... more Urban waste can be valorized within a biorefinery approach, producing platform chemicals, biopolymers and energy. In this framework, hydrodynamic cavitation (HC) is a promising pre-treatment for improving biodegradability due to its high effectiveness and low cost. This paper deals with the effect of HC pre-treatment on the acidogenic co-fermentation process of thickened sewage sludge from a WWTP and seasonal vegetable waste from a wholesale market. Specifically, HC was assessed by testing two sets of parameters (i.e., treatment time of 30 and 50 min; vacuum pressure 1.4 and 2.0 bar; applied power 8 and 17 kW) to determine its effectiveness as a pre-treatment of the mixture. The highest increase in sCOD (+83%) and VFAs (from 1.93 to 17.29 gCODVFA L-1) was gained after 50 min of cavitation. Fermentations were conducted with not cavitated and cavitated mixtures at 37 °C on 4 L reactors in batch mode, then switched to semi-continuous with OLR of 8 kgTVS m-3 d-1 and HRT of 5-6.6 d. Good VFAs concentrations (12.94-18.27 gCODVFA L-1) and yields (0.44-0.53 gCODVFA gVS(0)-1) were obtained, which could be enhanced by pre-treatment optimization and pH control. The organic acid rich broth obtained was then assessed as a substrate for PHAs storage by C. necator. It yielded 0.37 g g-1 of polyhydroxybutyrate, such biopolymer resulted to have analogous physicochemical characteristics of commercial equivalent. The only generated side-stream would be the solid-rich fraction of the fermented effluent, which valorization was assessed through BMP tests, showing a higher SGP of 0.42 Nm3 kgTVS-1 for the cavitated.
VIII INTERNATIONAL CONFERENCE ON “TIMES OF POLYMERS AND COMPOSITES”: From Aerospace to Nanotechnology, 2016
The Diels–Alder reaction between furan and maleimide moieties is a well-known and widely used str... more The Diels–Alder reaction between furan and maleimide moieties is a well-known and widely used strategy to build bio-based macromolecular structures with peculiar properties. The furan-maleimide adducts are thermally reversible because they can be broken above about 120°C and recombined at lower temperatures. At the moment only the monomers exhibiting the furan or the maleimide moieties on their extremity are used in order to get linear or cross-linked polymeric structures. The innovative idea described here consists in using a monomer bearing two carboxylic acidic groups on its extremities and a furan-maleimide Diels-Alder adduct within its structure. This monomer can give rise to classical polycondensation reactions leading to polymers. These polymers (which are polyesters in the present case) can be broken at high temperatures in correspondence of the furane-maleimide Diels-Alder adduct leading to segments exhibiting furan or maleimide moieties at their extremities, which at lower temperature recombine ...
The depletion of fossil resources and the growing demand for plastic waste reduction has put indu... more The depletion of fossil resources and the growing demand for plastic waste reduction has put industries and academic researchers under pressure to develop increasingly sustainable packaging solutions that are both functional and circularly designed. In this review, we provide an overview of the fundamentals and recent advances in biobased packaging materials, including new materials and techniques for their modification as well as their end-of-life scenarios. We also discuss the composition and modification of biobased films and multilayer structures, with particular attention to readily available drop-in solutions, as well as coating techniques. Moreover, we discuss end-of-life factors, including sorting systems, detection methods, composting options, and recycling and upcycling possibilities. Finally, regulatory aspects are pointed out for each application scenario and end-of-life option. Moreover, we discuss the human factor in terms of consumer perception and acceptance of upcyc...
The use of bioplastic mulch in agriculture has increased dramatically in the last years throughou... more The use of bioplastic mulch in agriculture has increased dramatically in the last years throughout the world. Nowadays, biodegradable materials for mulching films strive to constitute a reliable and more sustainable alternative to classical materials such as polyethylene (PE). The main challenge is to improve their durability in the soil to meet the required service length for crop farming by using benign and sustainable antioxidant systems. Here, we report the design and fabrication of biodegradable materials based on polybutylene (succinate adipate) (PBSA) for mulching applications, incorporating a fully biobased polymeric antioxidant deriving from ferulic acid, which can be extracted from an industrial by-product. Poly-dihydro (ethylene ferulate) (PHEF) from ferulic acid was synthesized by a two-step polymerization process. It is characterized by improved thermal stability in comparison with ferulic acid monomer and therefore suitable for common industrial processing conditions. ...
2,5‐Furandicarboxylic acid (FDCA) is currently considered one of the most relevant bio‐sourced bu... more 2,5‐Furandicarboxylic acid (FDCA) is currently considered one of the most relevant bio‐sourced building blocks, representing a fully sustainable competitor for terephthalic acid as well as the main component in green polymers such as poly(ethylene 2,5‐furandicarboxylate) (PEF). The oxidation of biobased 5‐hydroxymethylfurfural (HMF) represents the most straightforward approach to obtain FDCA, thus attracting the attention of both academia and industries, as testified by Avantium with the creation of a new plant expected to produce 5000 tons per year. Several approaches allow the oxidation of HMF to FDCA. Metal‐mediated homogeneous and heterogeneous catalysis, metal‐free catalysis, electrochemical approaches, light‐mediated procedures, as well as biocatalytic processes share the target to achieve FDCA in high yield and mild conditions. This Review aims to give an up‐to‐date overview of the current developments in the main synthetic pathways to obtain FDCA from HMF, with a specific fo...
Urban waste can be valorized within a biorefinery approach, producing platform chemicals, biopoly... more Urban waste can be valorized within a biorefinery approach, producing platform chemicals, biopolymers and energy. In this framework, hydrodynamic cavitation (HC) is a promising pre-treatment for improving biodegradability due to its high effectiveness and low cost. This paper deals with the effect of HC pre-treatment on the acidogenic co-fermentation process of thickened sewage sludge from a WWTP and seasonal vegetable waste from a wholesale market. Specifically, HC was assessed by testing two sets of parameters (i.e., treatment time of 30 and 50 min; vacuum pressure 1.4 and 2.0 bar; applied power 8 and 17 kW) to determine its effectiveness as a pre-treatment of the mixture. The highest increase in sCOD (+83%) and VFAs (from 1.93 to 17.29 gCODVFA L-1) was gained after 50 min of cavitation. Fermentations were conducted with not cavitated and cavitated mixtures at 37 °C on 4 L reactors in batch mode, then switched to semi-continuous with OLR of 8 kgTVS m-3 d-1 and HRT of 5-6.6 d. Good VFAs concentrations (12.94-18.27 gCODVFA L-1) and yields (0.44-0.53 gCODVFA gVS(0)-1) were obtained, which could be enhanced by pre-treatment optimization and pH control. The organic acid rich broth obtained was then assessed as a substrate for PHAs storage by C. necator. It yielded 0.37 g g-1 of polyhydroxybutyrate, such biopolymer resulted to have analogous physicochemical characteristics of commercial equivalent. The only generated side-stream would be the solid-rich fraction of the fermented effluent, which valorization was assessed through BMP tests, showing a higher SGP of 0.42 Nm3 kgTVS-1 for the cavitated.
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Papers by Claudio Gioia