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This work represents an innovative study that, for the first time, explores the possibility to use waste flours to produce thermoplastic polymeric bio-films. To the best of our knowledge, this is the first time that waste flours, derived from bakeries, pizzerias or pasta factories, have been proposed for the production of bio-polymers, as a replacement of neat starch. To this aim, durum waste flour derived from a pasta factory, soft waste flour derived from pizzerias and neat maize starch used as control material were firstly analyzed from dimensional, morphological and chemical points of view. Afterwards, waste flour films were produced by the addition of a nature-based plasticizer, glycerol. Mechanical characterization of the plasticized thermoplastic films, produced by compression molding, evidenced low performances, even in the case of the neat maize starch. In order to improve the mechanical properties, the possibility to include polylactic acid and cardanol-based plasticizer was also investigated. Mass transport properties of all the produced bio-films were investigated by measuring their water vapor permeability and hygroscopic absorption. The durability properties of the bio-films were assessed by accelerated ageing tests, while the bio-degradability of the waste-based films was evaluated by measuring the solubility and the degradation in water. The physicochemical analyses of the novel bio-films evidenced good mechanical properties, specifically, the waste-based films showed a lower hygroscopic absorption and water solubility than those of the blends containing neat starch.

This work is aimed to study the suitability of cardanol and its derivatives as plasticizers for poly(lactic acid), PLA. Differential scanning calorimetry (DSC) was used to assess the plasticizing effectiveness of cardanol (CARD) and its derivatives, cardanol acetate and epoxidated cardanol acetate, comparing the results with those obtained with a commercially available plasticizer, poly (ethylene glycol), PEG, with an average molecular weight of 400 g mol−1. Measurement of the glass transition temperature highlighted that, among the tested cardanol derivatives, neat cardanol is the most effective plasticizer for PLA. In fact, the glass transition temperature of PLA plasticized by CARD is only slightly higher than that of PLA plasticized by PEG. This is attributed to the lower compatibility between PLA and CARD compared to PLA and PEG, as estimated by the interaction radius. Therefore, cardanol could represent a technically valid, economic, and largely available plasticizer for PLA. Moreover, DSC, an X-ray diffraction analysis, showed that, compared to PEG, the addition of CARD involves a limited increase of the rate of crystallization, even in this case, due to its lower compatibility with PLA. Dynamic mechanical analysis showed that, below glass transition, PEG is able to reduce the stiffness of PLA by a higher extent. However, as the temperature increases, retention of the shear modulus of PEG-plasticized PLA is much higher than that of CARD-plasticized PLA. As a consequence, above glass transition, the stiffness of CARD-plasticized PLA becomes lower than that of PEG-plasticized PLA. Therefore, despite its lower compatibility with PLA, CARD can impart to plasticized PLA lower modulus compared to PEG, when the plasticizer content is high enough to reduce the glass transition below room temperature.

This work is aimed to the development and property optimization of cardanol derived plasticizers. To this purpose, different plasticizers were produced though different epoxidation routes, characterized by low toxicological and environmental impact. The plasticizers are characterized by different yield of epoxidation of the alkyl chain double bonds. The properties of the cardanol derived plasticizers were compared to the properties of commercial plasticizers, either phthalates or natural derived. Mechanical properties of soft PVC plasticized by cardanol derivatives were shown to be comparable to those of PVC with commercial plasticizers. The plasticizing efficiency of cardanol derivatives was significantly improved by increasing the yield of epoxidation. Also, mechanical properties performed after ageing showed the excellent stability of the properties of the cardanol derived plasticizer characterized by the higher yield. Evaluation of the property retention index after ageing indicated that such plasticizers showed an improved stability of properties compared to other commercial plasticizer. The results obtained highlight the relevance of an high conversion of the double bonds into epoxies in order to produce high quality plasticizers.

This work is aimed at studying the suitability of polylactic acid (PLA) plasticized by two cardanol derivatives, i.e., cardanol and epoxidized cardanol acetate, in rotational molding, for the production of hollow items. For this purpose, plasticized PLA samples were obtained by melt mixing and then processed by a lab-scale rotational molding equipment. For comparison, poly(ethylene glycole), PEG, and plasticized PLA samples were also produced. Despite the very low cooling rates attained in rotational molding, completely amorphous samples were obtained with neat PLA and PLA plasticized by cardanol derivatives. In contrast, PEG plasticized PLA showed a very high degree of crystallinity, as highlighted by DSC and XRD analysis, which made the extraction of the rotomolded box-shaped specimens impossible. The plasticizing effectiveness of cardanol derivatives was proven by tensile testing of rotational molded prototypes, which highlighted the reduced modulus and strength and improved strain to break, compared to neat PLA. Therefore, efficient toughening of PLA can be attained by the use of the two cardanol derived plasticizers, which involves a significant reduction of the polymer glass transition, as well as a reduced increase of the crystallization kinetic. On the other hand, the reduction of the glass transition temperature due to the addition of plasticizer is responsible for significant crystallization effects even during ageing at room temperature, which involves significant embrittlement of the material.

The aim of this work is the analysis of the suitability of cardanol derivatives as primary plasticizer for polyvinyl chloride (PVC). Cardanol derived plasticizers (CDP) were obtained by acetylation of cardanol, followed by epoxidation of the side chain double bonds. The developed procedures allowed to achieve high yields of acetylated cardanol, whereas plasticizers characterized by different yields of epoxidation were obtained, according to the used synthesis procedure. Rheological analysis was used in order to study the gelation process of PVC plastisols with CDP. A comparison of commercial phthalate and natural derived plasticizers showed that the CDP are characterized by adequate gelation properties, involving a complete absorption of the plasticizers at relatively low temperatures. The gelation properties showed a strong dependence on the yield of the epoxidation. In particular, lower gelation temperatures, higher plasticizer absorption and faster gelation were observed for higher epoxy content in the plasticizer. Finally, ageing tests were performed on soft PVC produced by the CDP. The weight loss of soft PVC with CDP is comparable to that of commercial plasticizers, particularly at high yields of epoxidation.