A sustainable approach toward mechanical recycling unsortable post-consumer WEEE: Reactive and non-reactive compatibilization.

While near-infrared (NIR) spectroscopy in post-consumer waste electrical and electronic equipment (WEEE) recycling accurately separates white or clear polymers, 40% containing dark plastics, termed 'unsortable WEEE,' are excluded from sorting lines and therefore incinerated or landfilled, causing environmental concerns. This study investigates the potential of using non-reactive and reactive copolymers as compatibilizers to enhance the performance of unsortable WEEE plastics free of brominated flame retardants. To the best of our knowledge, this is the first time that such copolymers have been explored as a solution for improving the compatibility of unsortable WEEE polymer blends. Initial trials with 4% of styrene-ethylene-butylene-styrene copolymer (SEBS-13) and SEBS-30-g-(maleic anhydride) copolymer (SEBS-30-g-MA MA) as compatibilizers showed insufficient results compared to virgin commercial polymers. However, the addition of higher concentrations of compatibilizers (i.e. up to 20 wt%) and the use of a SEBS having a higher styrene content (i.e. SEBS-30) improved the mechanical properties of the material, causing it to transition from brittle to ductile. This behavior was found more pronounced for the 20% non-reactive SEBS-30, for which the SEM analysis showed reduced phase segregation and revealed a more homogeneous fracture surface. This was further supported by Differential Scanning Calorimetry (DSC) analysis, which showed evidence of an interaction between one or more polymer phases. With a room temperature performance equivalent to that of virgin conventional polymers, the SEBS-30 compatibilization approach has made it possible to consider using unsortable WEEE streams as recycled materials in commercial applications.

Super toughened blends of poly(lactic acid) and poly(butylene adipate-co-terephthalate) injection-molded foams via enhancing interfacial compatibility and cellular structure.

Biodegradable poly(lactic acid) (PLA) foams have drawn increasing attention due to environmental challenges and petroleum crisis. However, it still remains a challenge to prepare PLA foams with fine cellular structures and high impact property, which significantly hinders its widespread application. Herein, phase interface-enhanced PLA/ poly(butylene adipate-co-terephthalate) (PBAT) blend foam, modified by a reactive compatibilizer through a simple reactive extrusion, was produced via a core-back foam injection molding technique. The obtained PLA blend foams displayed an impact strength as high as 49.1 kJ/m2, which was 9.3 and 6.4 times that of the unmodified PLA/PBAT blend and its corresponding foam, respectively. It proved that the interfacial adhesion and cell size both strongly affected the impact strength of injection-molded PLA/PBAT foams, and two major conclusions were proposed. First, enhancing interfacial adhesion could cause a brittle-tough transition of PLA/PBAT foams. Additionally, for foams with high interfacial adhesion, small cell size (<12 µm) was more favorable for the stretching of cells and extension of the whitened region in comparison with big cell size (cell size >60 µm), leading to the drastic toughening of PLA blends. This study provides a feasible, industrially scalable and practical strategy to prepare super toughened and fully biodegradable PLA materials.

The Effect of Epoxidized Soybean Oil on the Physical and Mechanical Properties of PLA/PBAT/PPC Blends by the Reactive Compatibilization.

Poly (lactic acid) (PLA)/poly (butylene adipate-co-terephthalate) (PBAT)/poly (propylene carbonate) (PPC) multi-phase blends were prepared by melt processing technique under the presence of compatibilizer with various composition. The effect on the physical and the mechanical property with/without ESO was characterized with spectrophotometric analysis, mechanical properties, thermal properties, rheological properties and barrier properties, and the structure-properties relationship was assessed. ​​The functional groups of PPC were found to effective to improve an interaction with carboxyl/hydroxyl group of PLA/PBAT binary blends to enhance the mechanical and physical properties on multi-phase blend system. The presence of PPC in PLA/PBAT blend affected the reduction of voids on the interface phase resulting in enhancing the oxygen barrier properties. With addition of ESO, the compatibility of ternary blend was found to be enhanced since the epoxy group of ESO reacted with the carboxyl/hydroxyl group of PLA, PBAT, and PPC, and under the condition with critical content of 4 phr of ESO, the elongation behavior dramatically increased as compared to that of blends without ESO while affecting reduction of oxygen barrier properties. The effect of ESO as a compatibilizer was clearly observed from the overall performances of ternary blends, and the potential feasibility of the PLA/PBAT/PPC ternary blends as packaging materials was confirmed at this study.

Fully biobased poly(lactic acid)/lignin composites compatibilized by epoxidized natural rubber.

Biobased poly(lactic acid)/lignin (PLA/lignin) composites are limited by poor mechanical properties resulted from poor compatibility and low interfacial adhesion. Herein, we reported a novel approach to improve compatibility and interfacial adhesion of PLA/lignin composites via reactive compatibilization with epoxidized natural rubber (ENR) as a compatibilizer. Interfacial tension calculation indicated that lignin tended to act as interfacial phase between PLA and ENR, but morphology analysis demonstrated lignin was wrapped with a layer of ENR and dispersed in PLA matrix, which was attributed to the interfacial reaction of ENR with both PLA and lignin. The interfacial reaction was confirmed by Fourier transform infrared spectroscopy. The compatibility and interfacial adhesion between PLA and lignin were improved significantly by incorporation and increase in the content of ENR, as evidenced by the reduced interfacial gaps, blurry phase boundaries, and enhanced elastic response. As such, the mechanical properties of PLA/lignin composites were enhanced significantly. The tensile strength and elongation at break of PLA/lignin (W/W, 80/20) were improved by 15 % and 77 %, respectively, with the incorporation of only 1 wt% ENR. We believe this approach to compatibilize PLA/lignin composites is promising because it would not require costly modification of lignin and would not compromise the sustainability of composites.

In-situ reactive compatiblization modified poly(l-lactic acid) and poly (butylene adipate-co-terephthalate) blends with improved toughening and thermal characteristics.

Triglycidyl isocyanurate (TGIC) with multifunctional epoxy is used for reactive compatibilization of Poly (l-lactic acid) (PLLA)/Poly (butylene adipate-co-terephthalate) (PBAT) blends. Interfacial tension, FTIR and SEM results show that TGIC has greater affinity and stronger reactivity with PBAT. The mixing sequence of PLLA/PBAT/TGIC blends has a significant impact on the compatibility. The TGIC and PBAT are reactive blended first, followed by the PLLA, which is most advantageous to produce a substantial amounts of branched copolymers PLLA-g-PBAT at the interface for the (PBAT/4%T) /PLLA blend. The considerable improvement of interfacial compatibility and the thickening of interfacial layer promote the stress transfer from the matrix to the dispersed PBAT phase. In comparison to PLLA/PBAT blend, the breaking elongation of (PBAT/4%T)/PLLA blend is raised by 25.6 times up to 164.2 % and the tensile strength is enhanced up to 32.1 MPa. The present work offers valuable perspectives on how to encourage the efficient application of reactive compatibilizers with epoxy groups in polyester blends.

Biodegradable blends from bacterial biopolyester PHBV and bio-based PBSA: Study of the effect of chain extender on the thermal, mechanical and morphological properties.

Being aware of the global problem of plastic pollution, our society is claiming new bioplastics to replace conventional polymers. Balancing their mechanical performance is required to increase their presence in the market. Brittleness of bacterial poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) was attempted to be decreased by melt blending with flexible starch-based poly(butylene succinate-co-butylene adipate) (PBSA). An epoxy-functionalized chain extender was used to enhance interaction between both immiscible biopolyesters. Mechanical performance, morphology, rheology, and crystallization behavior of injection-molded PHBV-PBSA blends (70-30, 50-50, and 30-70 wt%) were assessed in the presence and absence of the chain extender. Crystallization of PHBV was hindered, which was reflected in the improvement of mechanical properties. When PBSA >50 %, the homogeneity of results increased within the same sample while for PHBV-PBSA 70-30 wt% the elongation was 45 % higher. During the flexural test, it changed from brittle to non-breakable. The additive did not change the type of morphology developed by each blend nor the toughening mechanisms, so impact strength was barely affected. However, it reduced the size of dispersed phase domains due to a viscosity change, improving their processability. The higher the PHBV in the blend, the higher the effect of the chain extender.

Interfacial Engineering with Rigid Nanoplatelets in Immiscible Polymer Blends: Interface Strengthening and Interfacial Curvature Controlling.

The interfacial nanoparticle compatibilization (INC) strategy has opened up a promising avenue toward simultaneous functionalization and interfacial engineering of immiscible polymer blends. While the INC mechanism has been well developed recently, few investigations have focused on rigid nanoplatelets because of the inherent steric hindrance of the surface-grafted polymer chains. Herein, surface-modified rigid nanoplatelets have been incorporated into an immiscible poly(l-lactide) (PLLA)/poly(butylene succinate) (PBSU) blend. It is demonstrated that the strong interfacial adhesion between PLLA and PBSU phases is promoted via molecular entanglements of the grafted chains on the surface of nanoplatelets with the individual components. A refined phase morphology with improved mechanical properties can be achieved with the addition of 5 wt % modified Gibbsite nanoplatelets. It was further found that the stiffness of nanoplatelets can change the geometry of the interface significantly. It is, therefore, indicated that the simultaneous interface strengthening and interfacial curvature controlling of rigid nanoplatelets originate from the selective swelling/collapse of the in situ-formed PLLA and PBSU grafts within the corresponding phase at the interface. Such a mechanism is confirmed by the Monte Carlo simulations. This work provides new opportunities for the fabrication of advanced polymer blend nanocomposites.

Peroxide-Induced Synthesis of Maleic Anhydride-Grafted Poly(butylene succinate) and Its Compatibilizing Effect on Poly(butylene succinate)/Pistachio Shell Flour Composites.

Framing the Circular Bioeconomy, the use of reactive compatibilizers was applied in order to increase the interfacial adhesion and, hence, the physical properties and applications of green composites based on biopolymers and food waste derived lignocellulosic fillers. In this study, poly(butylene succinate) grafted with maleic anhydride (PBS-g-MAH) was successfully synthetized by a reactive melt-mixing process using poly(butylene succinate) (PBS) and maleic anhydride (MAH) that was induced with dicumyl peroxide (DCP) as a radical initiator and based on the formation of macroradicals derived from the hydrogen abstraction of the biopolymer backbone. Then, PBS-g-MAH was used as reactive compatibilizer for PBS filled with different contents of pistachio shell flour (PSF) during melt extrusion. As confirmed by Fourier transform infrared (FTIR), PBS-g-MAH acted as a bridge between the two composite phases since it was readily soluble in PBS and could successfully form new esters by reaction of its multiple MAH groups with the hydroxyl (-OH) groups present in cellulose or lignin of PSF and the end ones in PBS. The resultant compatibilized green composites were, thereafter, shaped by injection molding into 4-mm thick pieces with a wood-like color. Results showed significant increases in the mechanical and thermomechanical rigidity and hardness, meanwhile variations on the thermal stability were negligible. The enhancement observed was related to the good dispersion and the improved filler-matrix interfacial interactions achieved by PBS-g-MAH and also to the PSF nucleating effect that increased the PBS's crystallinity. Furthermore, water uptake of the pieces progressively increased as a function of the filler content, whereas the disintegration in controlled compost soil was limited due to their large thickness.

Improvement of PLLA Ductility by Blending with PVDF: Localization of Compatibilizers at Interface and Its Glycidyl Methacrylate Content Dependency.

In this work, the localization of reactive compatibilizer (RC, containing poly(methyl methacrylate) (PMMA) backbone with randomly distributed glycidyl methacrylate (GMA) on it) at the polyvinylidene fluoride/poly(l-lactic acid) (PVDF/PLLA) interface has been manipulated by means of GMA contents. At the very beginning of mixing, RC tends to stay in the PVDF phase due to the miscibility between PVDF and PMMA. Upon further shearing, more and more PLLA chains have been grafted on PMMA backbone, producing PLLA-g-PMMA copolymer. The balanced stress on two sides accounts for the localization of compatibilizers at the PVDF/PLLA interface. Finally, the stress of the PLLA side has been enhanced remarkably due to the higher graft density of PLLA, resulting in the enrichment of the copolymer in the PLLA matrix. The migration of RC from the PVDF phase to the immiscible interface and PLLA matrix can be accelerated by employing RC with higher GMA content. Furthermore, the compatibilizer localization produces a significant influence on the morphology and ductility of the PVDF/PLLA blend. Only when the compatibilizers precisely localize at the interface, the blend exhibits the smallest domain and highest elongation at break. Our results are of great significance for not only the fabrication of PLLA with high ductility, but also the precise localization of compatibilizers at the interface of the immiscible blend.