Thermoset materials and their composites are characterized by a long life cycle with their main applications in aircrafts, wind turbines and constructions as insulating materials. Considering the importance of recovery and valorization of these materials at their end-of-life, avoiding landfilling, the interest concerning their recycling grows continuously. The thermoset materials and their composites, to be successfully recovered and valorized, must degrade their three-dimensional structures and recover the mono-oligomers and/or fillers. The thermoset materials could successfully degrade through thermal treatment at different temperatures (for example, above 1000 °C for incineration, ca. 500 °C for oxidation/combustion of organic constituents, etc.), chemical degradation by catalyst, irradiation with or without the presence of water, alcohol, etc., and mechanical recycling, obtaining fine particles that are useful as filler and/or reinforcement additives. Among these recycling methods, this mini-review focuses on the formulation and recovery method of innovative thermoset with in-build recyclability, i.e., materials having chemical links that could be degraded on-demand or containing dynamic covalent bonds to have re-processable and/or recyclable thermoset. This issue could be considered the future perspective in developing novel thermoset materials. The aim of this review is to get an overview of the state of the art in thermoset recycling and of the most commonly used thermoset composites, recovering valuable reinforcing fibers. Additionally, in this work, we also report not only known recycling routes for thermoset and thermoset-based composites, but also new and novel formulating strategies for producing thermosets with built-in recyclability, i.e., containing chemical-triggered on-demand links. This mini-review is also a valuable guide for educational purposes for students and specialized technicians in polymer production and recycling.
Abstract. The polyhedral oligomeric silsesquioxane (POSS) additivated polystyrene (PS) based nanocomposites were prepared by melt processing and the structure-properties relationships of the POSS-PS systems were compared to those of the neat PS. In order to investigate the effect of these structural parameters on the final properties of the polymer nanocomposites, five different kinds of POSS samples were used, in particular, POSS with different inorganic cage and with different organic pendent groups. The rheological investigation suggests clearly that the POSS acts as a plasticizer and that the processability of the PS was positively modified. The affinity between the POSS samples and the PS matrix was estimated by the calculated theoretical solubility parameters, considering the Hoy's method and by morphology analysis. Minor difference between the solubility parameter of POSS and the matrix means better compatibility and no aggregation tendency. Furthermore, the POSS loading leads to a decrease of the rigidity, of the glass transition temperature and of the damping factor of the nanocomposite systems. The loading of different POSS molecules with open cage leads to a more pronounced effect on all the investigated properties that the loading of the POSS molecules with closed cage. Moreover, the melt properties are significantly influenced by the type of inorganic framework, by the type of the pendent organic groups and by the interaction between the POSS organic groups and the host matrix, while, the solid state properties appears to be influenced more by the kind of cage.
The introduction of antioxidants in polymers is the main way to prevent or delay the degradation process. In particular natural antioxidants receive attention in the food industry also because of their presumed safety. In this work bio-polymers, i.e. a commercial starch-based polymer (Mater-Bi®) and a bio-polyester (PLA), and a bio-polyether (PEO) were additivated with quercetin, a natural flavonoid antioxidants, in order to formulate bio-based films for ecosustainable packaging and outdoor applications. The photo-oxidation behavior of unstabilized and quercetin stabilized films was analyzed and compared with the behavior of films additivated with a commercial synthetic light stabilizer. The quercetin is able to slow down the photo-degradation rate of all bio-polymeric films investigated in similar way to the synthetic stabilize
Today’s world is at the point where almost everyone realizes the usefulness of going green. Due to so-called global warming, there is an urgent need to find solutions to help the Earth and move towards a green future. Many worldwide events are focusing on the global technologies in plastics, bioplastic production, the recycling industry, and waste management where the goal is to turn plastic waste into a trade opportunity among the industrialists and manufacturers. The present work aims to review the recycling process via analyzing the recycling of thermoplastic, thermoset polymers, biopolymers, and their complex composite systems, such as fiber-reinforced polymers and nanocomposites. Moreover, it will be highlighted how the frame of the waste management, increasing the materials specificity, cleanliness, and a low level of collected material contamination will increase the potential recycling of plastics and bioplastics-based materials. At the same time, to have a real and approachable trade opportunity in recycling, it needs to implement an integrated single market for secondary raw materials.
A new novel approach for the stabilisation of polymer-clay nanocomposites has been investigated based on reacting chemically an antioxidant function, a hindered phenol moiety, with an organic modifier based on a quaternary ammonium salt. The chemically linked antioxidant-containing organic modifier (AO-OM) was then introduced into natural montmorillonite (MMt) through a cation-exchange reaction resulting in antioxidant-containing organo-modified clay (AO-OM-MMt). The new antioxidant-containing modified clay, along with other organo-modified clays having a similar organo-modifier but without the reacted antioxidant, were characterised by spectroscopic, thermogravimetric and x-ray diffraction techniques and tested for their thermo-oxidative stability. PA11-based clay nanocomposites samples containing the AO-OM-MMt and the other organo-modified clays, both without and with an added (i.e. not chemically reacted) hindered phenol antioxidant (similar to the one used in the AO-OM) were prepared by melt processing and examined for their processing and long-term thermal-oxidative stability at high temperatures. It was shown that although the new organo-modifier, AO-OM, was also susceptible to the Hoffman elimination reaction, the nanocomposites containing this newly modified clay (PA11/AO-OM-MMt) showed higher melt processing and long-term thermo-oxidative stability, along with excellent clay dispersion and exfoliation, compared to the other PA11-nanocomposites examined here (with and without the conventionally added antioxidant). It is suggested here that the excellent overall performance observed for the PA11/AO-OM-MMt nanocomposites is due to an in-situ partial release of low molecular weight antioxidant species having stabilising functionalities that are capable of acting locally at the interface between the inorganic clay platelets and the polymeric matrix which is a critical area for the onset of degradation processes
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