An official website of the United States government
Abstract In this study, poly(ethylene terephthalate)‐block‐polyethylene (PET‐PE) multiblock copolymers (MBCPs) with block molar masses of ~4 or 7 kg mol−1and either alternating or random block sequencing, and a PE‐PET‐PE triblock copolymer (TBCP) of comparable total molar mass, were synthesized. To explore the effect of molecular architecture on compatibilization, both MBCPs and TBCPs were blended into 80/20 wt/wt mixtures of PET/linear low‐density PE (LLDPE). Compatibilization was remarkably efficient for all MBCP types, with the addition of 0.2 wt% yielding blends nearly as tough as PET homopolymer. Addition of MBCP also significantly decreases LLDPE dispersed phase sizes compared to PET/LLDPE neat blends, as much as 80% in as‐mixed blends and by a factor of 10 in post‐mixing thermally annealed samples. Conversely, the TBCP was less efficient at decreasing domain sizes of the blends and improving the mechanical properties, requiring loadings of 1 wt% to produce comparably tough blends. Peel tests of PET/BCP/LLDPE trilayer films showed that both MBCPs and TBCP all improve interfacial strength over a PET‐PE bilayer film by two orders of magnitude; however, when the BCPs were preloaded into LLDPE, only the MBCP containing films showed strong adhesion highlighting their potential utility as adhesive agents in multilayer films.
more »
« less
Mitigating Extrusion Instabilities and Enhancing Mechanical Performance of Post‐Consumer Recycled Polyolefins via Layer Multiplying Elements
ABSTRACT The processing and performance of multilayer films containing post‐consumer recycled polypropylene (rPP1 and rPP2) materials are investigated to understand the effect of layer multiplying elements (LMEs), die temperature, virgin polypropylene (vPP%) content, and polyethylene (PE) contamination in flexible packaging applications. Three‐layer coextruded films were created with virgin polypropylene (vPP) consistently applied as the outer layers while the core layer comprised recyclates with varying concentrations of polyethylene as an unintended contaminant to polypropylene. To enhance layer uniformity and interfacial interaction, a layer multiplying element (LME) was employed to increase the number of coextruded film layers from 3 to 9. Tensile properties (elongation at break, yield stress, and modulus) were characterized in both machine direction (MD) and transverse direction (TD); after which, multiple linear regression analyses were conducted on 45 observations to model the effect of each factor. The results indicated that the LME significantly enhanced elongation at break in TD by 1280% strain, while temperature and vPP fraction also contributed positively to ductility in TD (+341% and +2373%, respectively). However, PE contamination had a substantial negative impact on elongation in MD (−2449%) underscoring its embrittling role due to lack of compatibility with the PP matrix. Critically, LME partially mitigated the negative PE effect via an interaction term (PE*LME), improving elongation in MD by +3101%. Scanning Electron Microscopy (SEM) revealed a distinct, regular pattern of alternating polyethylene (PE) and polypropylene (PP) domains forming ribbon‐like fibrillar structures. This unique morphological arrangement suggests a self‐organizing behavior driven by immiscibility and flow‐induced alignment under extrusion conditions. The presence of regular alternating domains at near equal concentrations implies a balance among shear‐driven orientation, phase separation kinetics, and crystallization phenomena, resulting in an ordered micro‐fibrillar structure. Importantly, both monolayer and multilayer films containing rPP2 or rPP1/rPP2 blends exhibited these aligned, ribbon‐like fibrils oriented in the machine direction (MD). SEM analysis of fractured specimens further indicated that brittle failure was often associated with interfacial delamination, particularly in recyclate‐rich regions, whereas ductile failure exhibited entangled reinforcing fibrils, suggesting improved energy absorption and interlayer cohesion. Understanding and controlling this self‐organized microstructure could significantly enhance processing stability, mechanical properties, and potential applications of recycled polyolefin blends, offering novel strategies for tailoring recyclate morphology and performance.
more »
« less
- Award ID(s):
- 2118808
- PAR ID:
- 10640225
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Polymer Engineering & Science
- Volume:
- 65
- Issue:
- 11
- ISSN:
- 0032-3888
- Format(s):
- Medium: X Size: p. 5974-5991
- Size(s):
- p. 5974-5991
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Semicrystalline poly(l-lactide) (PLLA) is a leading biosourced, compostable alternative to conventional plastics but lacks sufficient toughness for many applications. Chain alignment via uniaxial stretching may be used to toughen PLLA but often creates anisotropic materials that are tough in the machine direction (MD) but brittle in the transverse direction (TD). This work reports uniaxially stretched films of PLLA blended with 3 wt % poly(ethylene oxide)-block-poly(butylene oxide) (PEO-PBO), which exhibit as much as a 5-fold increase in toughness in the TD compared to similarly stretched neat PLLA films─and elucidates the impact of PEO–PBO particles on the relationship between stretching, crystallization behavior, and resultant mechanical properties. Faster stretching rates were correlated with higher yield stress and a greater degree of crystallite alignment in the PEO–PBO/PLLA blends. This trend highlights the synergistic relationship between crystallinity and chain alignment and suggests a competing mechanism of heterogeneous crystallite nucleation around PEO–PBO particles. Importantly, PEO–PBO/PLLA exhibited a TD elongation at break of 36%, five times greater than the value of similarly stretched neat PLLA and even greater than the corresponding MD value of either material. Taken together, these findings demonstrate that uniaxial stretching of PEO–PBO/PLLA blends produces biaxially tough films, with the fastest stretching conditions producing the greatest enhancement in TD toughness.more » « less
-
Polymer blend compatibilization is an attractive solution for mechanical recycling of mixed plastic waste because it can result in tough blends. In this work, hydroxy-telechelic polyethylene (HOPEOH) reactive additives were used to compatibilize blends of polyethylene terephthalate (PET) and linear low-density polyethylene (LLDPE). HOPEOH additives were synthesized with molar masses of 1–20 kg/mol by ring-opening metathesis polymerization of cyclooctene followed by catalytic hydrogenation. Melt-compounded blends containing 0.5 wt % HOPEOH displayed reduced dispersed phase LLDPE particle sizes with ductilities comparable to virgin PET and almost seven times greater than neat blends, regardless of additive molar mass. In contrast, analogous blends containing monohydroxy PE additives of comparable molar masses did not result in compatibilization even at 2 wt % loading. The results strongly suggest that both hydroxy ends of HOPEOH undergo transesterification reactions during melt mixing with PET to form predominantly PET–PE–PET triblock copolymers at the interface of the dispersed and matrix phases. We hypothesize that the triblock copolymer compatibilizers localized at the interface form trapped entanglements of the PE midblocks with nearby LLDPE homopolymer chains by a hook-and-clasp mechanism. Finally, HOPEOH compounds were able to efficiently compatibilize blends derived solely from postconsumer PET and PE bottles and film, suggesting their industrial applicability.more » « less
-
Management of the plastic industry is a momentous challenge, one that pits enormous societal benefits against an accumulating reservoir of nearly indestructible waste. A promising strategy for recycling polyethylene (PE) and isotactic polypropylene ( i PP), constituting roughly half the plastic produced annually worldwide, is melt blending for reformulation into useful products. Unfortunately, such blends are generally brittle and useless due to phase separation and mechanically weak domain interfaces. Recent studies have shown that addition of small amounts of semicrystalline PE- i PP block copolymers (ca. 1 wt%) to mixtures of these polyolefins results in ductility comparable to the pure materials. However, current methods for producing such additives rely on expensive reagents, prohibitively impacting the cost of recycling these inexpensive commodity plastics. Here, we describe an alternative strategy that exploits anionic polymerization of butadiene into block copolymers, with subsequent catalytic hydrogenation, yielding E and X blocks that are individually melt miscible with PE and i PP, where E and X are poly(ethylene- ran -ethylethylene) random copolymers with 6 wt% and 90 wt% ethylethylene repeat units, respectively. Cooling melt blended mixtures of PE and i PP containing 1 wt% of the triblock copolymer EXE of appropriate molecular weight, results in mechanical properties competitive with the component plastics. Blend toughness is obtained through interfacial topological entanglements of the amorphous X polymer and semicrystalline i PP, along with anchoring of the E blocks through cocrystallization with the PE homopolymer. Significantly, EXE can be inexpensively produced using currently practiced industrial scale polymerization methods, offering a practical approach to recycling the world’s top two plastics.more » « less
-
Polymer blends offer a cost-effective way to create new materials with enhanced properties. However, blending different polymers often results in phase separation with weak interfacial adhesion, leading to inferior mechanical properties. Given that high-density polyethylene (HDPE) and isotactic polypropylene (iPP) are the largest volume polymers, there is significant interest in developing blends of these materials. Applying a singlet nitrene-facilitated dynamic crosslinking method recently developed in our lab, in this study we prepared a series of HDPE/iPP blends across a range of compositions with enhanced compatibility and tunable thermomechanical properties. By incorporating a small amount of a dynamic crosslinker featuring a siloxane core and bis-aromatic sulfonyl azides (bis-ASA) into varying compositions of HDPE and iPP, we achieve significant improvements in the compatibility. AFM and SEM imaging analyses reveal that the compatibilized blends exhibit superior homogeneity compared to control blends. Additionally, these blends show significant improvements in elongation at break, toughness, and oxidative stability. The dynamic crosslinking further enhances the blends’ creep resistance while retains reprocessability, paving the way for the development of tailorable polymer blends for various applications.more » « less
