New Functional Bionanocomposites by Combining Hybrid Host-Guest Systems with a Fully Biobased Poly(lactic acid)/Poly(butylene succinate-co-adipate) (PLA/PBSA) Binary Blend.

In this study, we have developed innovative polymer nanocomposites by integrating magnesium-aluminum layered double hydroxide (LDH)-based nanocarriers modified with functional molecules into a fully biobased poly(lactic acid)/poly(butylene succinate-co-adipate) (PLA/PBSA) matrix. These LDH-based hybrid host-guest systems contain bioactive compounds like rosmarinic acid, ferulic acid, and glycyrrhetinic acid, known for their antioxidant, antimicrobial, and anti-inflammatory properties. The bioactive molecules can be gradually released from the nanocarriers over time, allowing for sustained and controlled delivery in various applications, such as active packaging or cosmetics. The morphological analysis of the polymer composites, prepared using a discontinuous mechanical mixer, revealed the presence of macroaggregates and nano-lamellae at the polymer interface. This resulted in an enhanced water vapor permeability compared to the original blend. Furthermore, the migration kinetics of active molecules from the thin films confirmed a controlled release mechanism based on their immobilization within the lamellar system. Scaling-up experiments evaluated the materials' morphology and mechanical and thermal properties. Remarkably, stretching deformation and a higher shear rate during the mixing process enhanced the dispersion and distribution of the nanocarriers, as confirmed by the favorable mechanical properties of the materials.

Rosmarinic and Glycyrrhetinic Acid-Modified Layered Double Hydroxides as Functional Additives for Poly(Lactic Acid)/Poly(Butylene Succinate) Blends.

Immobilizing natural antioxidant and biologically active molecules in layered double hydroxides (LDHs) is an excellent method to retain and release these substances in a controlled manner, as well as protect them from thermal and photochemical degradation. Herein, we describe the preparation of host-guest systems based on LDHs and rosmarinic and glycyrrhetinic acids, two molecules obtained from the extraction of herbs and licorice root, respectively, with antioxidant, antimicrobial, and anti-inflammatory properties. Intercalation between the lamellae of the mono-deprotonated anions of rosmarinic and glycyrrhetinic acid (RA and GA), alone or in the presence of an alkyl surfactant, allows for readily dispersible systems in biobased polymer matrices such as poly(lactic acid) (PLA), poly(butylene succinate) (PBS), and a 60/40 wt./wt. PLA/PBS blend. The composites based on the PLA/PBS blend showed better interphase compatibility than the neat blend, correlated with increased adhesion at the interface and a decreased dispersed phase size. In addition, we proved that the active species migrate slowly from thin films of the composite materials in a hydroalcoholic solvent, confirming the optimization of the release process. Finally, both host-guest systems and polymeric composites showed antioxidant capacity and, in the case of the PLA composite containing LDH-RA, excellent inhibitory capacity against E. coli and S. aureus.

Surface Functionalization of Face Masks with Cold Plasma and Its Effect in Anchoring Polyphenols Extracted from Agri-Food.

To improve the capability of non-woven polypropylene-based fabric (NWF-PP) used for face mask production to retain active biomolecules such as polyphenols, the surface functionalization of NWF-PP-directly cut from face masks-was carried out by employing cold plasma with oxygen. The nature/structure of the functional groups, as well as the degree of functionalization, were evaluated by ATR-FTIR and XPS by varying the experimental conditions (generator power, treatment time, and oxygen flow). The effects of plasma activation on mechanical and morphological characteristics were evaluated by stress-strain measurements and SEM analysis. The ability of functionalized NWF-PP to firmly anchor polyphenols extracted from cloves was estimated by ATR-FTIR analysis, IR imaging, extractions in physiological solution, and OIT analysis (before and after extraction), as well as by SEM analysis. All the results obtained converge in showing that, although the plasma treatment causes changes-not only on the surface-with certain detriment to the mechanical performance of the NWF-PP, the incorporated functionalities are able to retain/anchor the active molecules extracted from the cloves, thus stabilizing the treated surfaces against thermo-oxidation even after prolonged extraction.

Binary Green Blends of Poly(lactic acid) with Poly(butylene adipate-co-butylene terephthalate) and Poly(butylene succinate-co-butylene adipate) and Their Nanocomposites.

Poly(lactic acid) (PLA) is the most widely produced biobased, biodegradable and biocompatible polyester. Despite many of its properties are similar to those of common petroleum-based polymers, some drawbacks limit its utilization, especially high brittleness and low toughness. To overcome these problems and improve the ductility and the impact resistance, PLA is often blended with other biobased and biodegradable polymers. For this purpose, poly(butylene adipate-co-butylene terephthalate) (PBAT) and poly(butylene succinate-co-butylene adipate) (PBSA) are very advantageous copolymers, because their toughness and elongation at break are complementary to those of PLA. Similar to PLA, both these copolymers are biodegradable and can be produced from annual renewable resources. This literature review aims to collect results on the mechanical, thermal and morphological properties of PLA/PBAT and PLA/PBSA blends, as binary blends with and without addition of coupling agents. The effect of different compatibilizers on the PLA/PBAT and PLA/PBSA blends properties is here elucidated, to highlight how the PLA toughness and ductility can be improved and tuned by using appropriate additives. In addition, the incorporation of solid nanoparticles to the PLA/PBAT and PLA/PBSA blends is discussed in detail, to demonstrate how the nanofillers can act as morphology stabilizers, and so improve the properties of these PLA-based formulations, especially mechanical performance, thermal stability and gas/vapor barrier properties. Key points about the biodegradation of the blends and the nanocomposites are presented, together with current applications of these novel green materials.

Dispersion of Few-Layer Black Phosphorus in Binary Polymer Blend and Block Copolymer Matrices.

Exfoliated black phosphorus (bP) embedded into a polymer is preserved from oxidation, is stable to air, light, and humidity, and can be further processed into devices without degrading its properties. Most of the examples of exfoliated bP/polymer composites involve a single polymer matrix. Herein, we report the preparation of biphasic polystyrene/poly(methyl methacrylate) (50/50 wt.%) composites containing few-layer black phosphorus (fl-bP) (0.6-1 wt.%) produced by sonicated-assisted liquid-phase exfoliation. Micro-Raman spectroscopy confirmed the integrity of fl-bP, while scanning electron microscopy evidenced the influence of fl-bP into the coalescence of polymeric phases. Furthermore, the topography of thin films analyzed by atomic force microscopy confirmed the effect of fl-bP into the PS dewetting, and the selective PS etching of thin films revealed the presence of fl-bP flakes. Finally, a block copolymer/fl-bP composite (1.2 wt.%) was prepared via in situ reversible addition-fragmentation chain transfer (RAFT) polymerization by sonication-assisted exfoliation of bP into styrene. For this sample, 31P solid-state NMR and Raman spectroscopy confirmed an excellent preservation of bP structure.

Agri-Food Extracts Effectiveness in Improving Antibacterial and Antiviral Properties of Face Masks: A Proof-of-Concept Study.

The European dependencies for raw materials supply from foreign countries have been unquestionably shown by COVID-19 outbreak and have become particular evident from the slow response to the need for high quality personal protective equipment (PPEs). Among all medical devices, surgical face masks have earned themselves a primary role for the containment of the epidemic. In this context, our work aims at improving the barrier effect of surgical mask by depositing on their external surface a mixture of bioactive compounds, mainly polyphenols, extracted from agronomical sources. The main objective is the integration of the biorefining of agri-food solid wastes with the potential virucidal properties of the polyphenolic extracts for the treatment of PPEs.

Macromolecular Dyes by Chromophore-Initiated Ring Opening Polymerization of L-Lactide.

End functionalized polylactides are prepared by ring opening polymerization of L-lactide in the presence of stannous octoate (Sn(Oct)2). Three chromophores, 9H-carbazol-ethanol (CA), 9-fluorenyl-methanol (FM), and 2-(4-(2-chloro-4-nitrophenylazo)-N-ethylphenylamino)ethanol (Disperse Red 13, DR), are for the first time used as co-initiators in the polymerization process. The polymerization reaction is initiated by conventional thermal treatment, but in the case of FM, microwave-assisted polymerization is also carried out. CA and FM absorb and emit in the UV portion of the electromagnetic spectrum, whereas DR absorbs in the visible part. The obtained end-capped polylactides derivatives show the same photophysical properties as the initiator, so they are "macromolecular dyes" (MDs) that can be used "as synthesized" or can be blended with commercial poly(lactic acid) (PLA). The blends of PLA with MDs have ultraviolet-visible (UV-Vis) absorption and fluorescence emission features similar to that of MDs and thermal properties typical of PLA. Finally, migration tests, carried out onto the blends of PLA with MDs and PLA with free chromophores, show that MDs are less released than free chromophores both in solution and in the solid phase.

A Perspective on Recent Advances in Phosphorene Functionalization and Its Applications in Devices.

Phosphorene, the 2D material derived from black phosphorus, has recently attracted a lot of interest for its properties, suitable for applications in materials science. The physical features and the prominent chemical reactivity on its surface render this nanolayered substrate particularly promising for electrical and optoelectronic applications. In addition, being a new potential ligand for metals, it opens the way for a new role of the inorganic chemistry in the 2D world, with special reference to the field of catalysis. The aim of this review is to summarize the state of the art in this subject and to present our most recent results in the preparation, functionalization, and use of phosphorene and its decorated derivatives. We discuss several key points, which are currently under investigation: the synthesis, the characterization by theoretical calculations, the high pressure behavior of black phosphorus, as well as its decoration with nanoparticles and encapsulation in polymers. Finally, device fabrication and electrical transport measurements are overviewed on the basis of recent literature and the new results collected in our laboratories.

Polymer-Based Black Phosphorus (bP) Hybrid Materials by in Situ Radical Polymerization: An Effective Tool To Exfoliate bP and Stabilize bP Nanoflakes.

Black phosphorus (bP) has been recently investigated for next generation nanoelectronic multifunctional devices. However, the intrinsic instability of exfoliated bP (the bP nanoflakes) toward both moisture and air has so far overshadowed its practical implementation. In order to contribute to fill this gap, we report here the preparation of new hybrid polymer-based materials where bP nanoflakes (bPn) exhibit a significantly improved stability. The new materials have been prepared by different synthetic paths including: (i) the mixing of conventionally liquid-phase exfoliated bP (in dimethyl sulfoxide, DMSO) with poly(methyl methacrylate) (PMMA) solution; (ii) the direct exfoliation of bP in a polymeric solution; (iii) the in situ radical polymerization after exfoliating bP in the liquid monomer (methyl methacrylate, MMA). This last methodology concerns the preparation of stable suspensions of bPn-MMA by sonication-assisted liquid-phase exfoliation (LPE) of bP in the presence of MMA followed by radical polymerization. The hybrids characteristics have been compared in order to evaluate the bP dispersion and the effectiveness of the bPn interfacial interactions with polymer chains aimed at their long-term environmental stabilization. The passivation of the bPn is particularly effective when the hybrid material is prepared by in situ polymerization. By using this synthetic methodology, the nanoflakes, even if with a gradient of dispersion (size of aggregates), preserve their chemical structure from oxidation (as proved by both Raman and 31P-solid state NMR studies) and are particularly stable to air and UV light exposure. The feasibility of this approach, capable of efficiently exfoliating bP while protecting the bPn, has been then verified by using different vinyl monomers (styrene and N-vinylpyrrolidone), thus obtaining hybrids where the nanoflakes are embedded in polymer matrices with a variety of intriguing thermal, mechanical, and solubility characteristics.

Grafting of Hindered Phenol Groups onto Ethylene/α-Olefin Copolymer by Nitroxide Radical Coupling.

The covalent immobilization of hindered phenol groups, with potential antioxidant activity, onto an ethylene/α-olefin (EOC) copolymer was carried out by the nitroxide radical coupling (NRC) reaction performed in the melt with a peroxide and the 3,5-di-tert-butyl-4-hydroxybenzoyl-2,2,6,6-tetramethylpiperidine-1-oxyl radical (BHB-T). Functionalized EOC (EOC-g-(BHB-T)) was exposed to photo- and thermo-oxidation. By comparison with some model compounds bearing the (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) moiety or the hindered phenol unit, it was observed that the grafted BHB-T could effectively help the stabilization of the polymer matrix both under photo- and thermo-oxidation. In addition, the immobilization of BHB-T can effectively increase the service life of the functionalized polymers when polymer films were put in contact with ethanol solution thus simulating a possible application of the modified polymer.

Structural, thermal and photo-physical data of azo-aromatic TEMPO derivatives before and after their grafting to polyolefins.

The data reported in this paper are complementary to the characterization of 4-(phenylazo)-benzoyl-2,2,6,6-tetramethylpiperidine-1-oxyl radical (AzO-TEMPO) and of the 4-(2-thienylazo)-benzoyl-2,2,6,6-tetramethylpiperidine-1-oxyl radical (ThiO-TEMPO) before and after their grafting to two polyethylene matrices (a copolymer ethylene/α-olefin (co-EO) and a high density polyethylene (HDPE)). Particularly the data reported in this paper confirm the structure (FT-IR analysis), the thermal (TGA and EPR) and the photo-physical (UV-vis) properties of the RO-TEMPO derivatives before and after their grafting. Herein, the FT-IR spectrum and TGA thermogram of ThiO-TEMPO were compared with those of AzO-TEMPO. Moreover, the superimposition of UV-vis spectra collected during the irradiation under 366 or 254 nm emitting lamp of AzO-TEMPO and ThiO-TEMPO in acetonitrile solution are reported. Finally, a complete DSC characterization of the functionalized POs is shown. DOI of original article: 〈http://dx.doi.org/10.1016/j.polymer.2015.11.018〉 [1].

Preparation and testing of a solid secondary plasticizer for PVC produced by chemical degradation of post-consumer PET.

Post-consumer poly(ethylene therephthalate) (PET) obtained from milled water bottles was chemically degraded by glycolysis, using suitable amounts of diethylene glycol (DEG) and Ca/Zn stearate as catalyst system. The process was carried out by employing a melt mixer as the chemical reactor, which is the facility generally used for plastic compounding. The degraded PET products were first characterized from structural and thermal point of view by Fourier transform infrared spectroscopy (FTIR), Proton nuclear magnetic resonance ((1)H NMR), Size exclusion chromatography (SEC) Differential scanning calorimetry (DSC) and Thermogravimetric analysis (TGA), and thereafter used alone or together with di(2-ethylhexyl) phthalate (DEHP) in poly(vinyl chloride) PVC formulations. The plasticization was, in fact, accomplished by using a binary system consisting of DEHP as primary plasticizer and a degraded PET product as secondary plasticizer (SP). The obtained materials were characterized through the main methods used to assess flexible PVC compounds: hardness in Shore A scale, thermal properties and quantitative migration of the plasticizer. The solid secondary plasticizer obtained from post-consumer PET improves both the processing characteristics and the thermal stability of the final flexible PVC compounds while maintaining their hardness within the top values of the Shore A scale. In addition, a considerable reduction of the plasticizers migration (23%) was obtained by optimizing the formulation.

Morphology development and stability of polypropylene/organoclay nanocomposites.

A series of polypropylene (PP)/organoclay nanocomposites with varied concentrations of clay, from 1 to 7 wt%, was successfully prepared via melt intercalation using a PP functionalized with maleic anhydride as compatibilizer. The morphology/property relationships of the nanocomposites were investigated by XRD, TGA and DSC analyses. Two distinct groups of composites, from a quasi-exfoliated to an intercalated/flocculated morphology, were identified. In particular, intercalated/flocculated morphologies were obtained for those composites with an organoclay concentration beyond the threshold (3 wt%), as evidenced by XRD analysis and confirmed by the increase of the glass transition temperature. This last effect was related to the confinement of polymer chains between the silicate layers, generating a reduction of the chain mobility. The variable increase of the thermal stability of the nanocomposites was also likely related to the different degree of exfoliation/intercalation of the samples. The toluene extraction of composites was used as a powerful methodology to distinguish between polymer phases differently interacting with the inorganic surface: composites having a semi-exfoliated structure were split into two fractions having a similar morphology. For those samples having the higher organoclay concentration and intercalated morphology, a toluene-residue fraction was obtained containing almost all the clay present in the pristine composite. Furthermore, in this case the morphological analysis of the residue fraction evidenced a collapse of the inorganic structure compared to that of the unextracted composite. A careful characterization of both soluble and residue fractions is reported and the results are discussed considering the interactions at the interface between the functionalized PP chains and silicate layers and their effects on the organoclay dispersion degree and stability.

New functionalized polypropylenes as controlled architecture compatibilizers for polypropylene layered silicates nanocomposites.

Polypropylene (PP) samples functionalized with Maleic Anhydride (MAH) were used as interfacial coupling agents during the preparation of PP based layered silicate nanocomposites (PP-LSN). To prepare these functionalized PP samples, butyl 3-(2-furyl)propenoate (BFA) was used as coagent during the radical post-functionalization with MAH to avoid the polymer degradation. The obtained materials, differing from the functionalization degree (FD) and structure (MW and molecular weight distribution), were accurately characterized and firstly employed as polymer matrices for PP-LSN preparation to study the influence of their architecture on clay dispersion and thus on their intercalation capability. Successively, PP-LSNs were prepared by using PP as matrix and 5 phr of the above compatibilizers. Morphological, thermal, mechanical and thermo-mechanical analyses of the nanocomposites pointed out that the higher molecular weight PP-g-MAH samples allow to achieve simultaneously a good intercalation within the filler and a significant compatibilization with pristine PP chains, leading to high performances PP-LSNs.

Organophilic Boehmite nanoparticles by ATRP methacrylates polymerization: synthesis, characterization and dispersion in polypropylene.

Boehmite nanoparticles covered with a polymer shell enhancing the organophilicity of the surface were prepared by physical adsorption of a polyelectrolyte atom transfer radical polymerization (ATRP) macroinitiator followed by graft-polymerization of methyl methacrylate or 2-hydroxyethyl methacrylate. The presence of polymer chains adsorbed/grafted on the Boehmite was confirmed by attenuated total reflection infrared (ATR-IR) spectroscopy and by thermo-gravimetric analysis (TGA), which showed a significant amount of polymer covering the particles. The methodology of polymerization and the kinetics suggested the possibility to modulate the amount, type and thickness of grafted polymer shell. These organic-inorganic hybrid materials were melt compounded in a Brabender mixer with isotactic polypropylene in the presence of functionalized polypropylene. The dispersion degree of Boehmite nanoparticles in the polypropylene matrix as well as their reinforcing effect were studied by morphology characterization [scanning electron microscopy (SEM) and X-ray diffraction (XRD)], whereas thermal and thermo-mechanical properties were assessed by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA).