Imperfect sorting of mixed plastic waste in mechanical recycling processes often results in phase-separated polymer blends that are brittle and no longer suitable for the applications served by the virgin materials. Through compatibilization, phase-separated blends can exhibit properties in between their constituent homopolymers, making them more attractive and valuable. In this work, we develop a deeper understanding of reactive blend compatibilization using hydroxy telechelic polyethylene additives in blends of glycol-modified polyethylene terephthalate and polyethylene. A series of staged mixing experiments (i.e., premixing in either phase vs. single batch mixing) at temperatures ranging from 210 degrees C to 270 degrees C suggests that preformation of copolymer is key for successful compatibilization of this system at lower temperatures, as determined by tensile testing and imaging of the macro-phase separated structure. Copolymer formation as a function of mixing time and temperature was estimated using differential scanning calorimetry, yielding an estimated activation energy of around 89 kJ/mol, similar to previously reported values for transesterification reactions. In total, this work provides an understanding of both the mechanism and limitations of reactive telechelic PE additives as compatibilizers in polymer blend systems.

Cross-linked polyolefins have important advantages over their thermoplastic analogues, particularly improved impact strength and abrasion resistance, as well as increased chemical and thermal stability; however, most strategies for their production involve postpolymerization cross-linking of polyolefin chains. Here, a tandem ring-opening metathesis polymerization (ROMP)/hydrogenation approach is presented. Cyclooctene (COE)-co-dicyclopentadiene (DCPD) networks are first synthesized using ROMP, after which the dispersed Ru metathesis catalyst is activated for hydrogenation through the addition of hydrogen gas. The reaction temperature for hydrogenation must be sufficiently high to allow mobility within the system, as dictated by thermal transitions (i.e., glass and melting transitions) of the polymeric matrix. COE-rich materials exhibit branched-polyethylene-like crystallinity (25% crystallinity) and melting points (Tm = 107 °C), as well as excellent ductility (>750% extension), while majority DCPD materials are glassy (Tg = 84 °C) and much stiffer (E = 710 MPa); all materials exhibit high tensile toughness. Importantly, hydrogenation of olefins in these cross-linked materials leads to notable improvements in oxidative stability, as saturated networks do not experience the same substantial degradation of mechanical performance as their unsaturated counterparts upon prolonged exposure to air.

Reactive compatibilization is an attractive solution to improve the mechanical properties of polymer blends that inherently result from plastic recycling processes. In this study, pendant hydroxy polyethylene reactive additives were synthesized through ring-opening metathesis polymerization (ROMP) and their ability to compatibilize poly(ethylene terephthalate) (PET)/polyethylene blends through reactive compatibilization was evaluated. The ROMP synthesis strategy enabled the deconvolution of the effects of overall number-average molar mass (M n) and average molar mass between reactive hydroxy groups (M g) on compatibilization effectiveness. The results of this study suggest a near-optimal M g similar to 1 kg/mol where the strain at break (epsilon b) of the blend with 1 wt % additive is increased significantly (epsilon b similar to 280%) over the neat blend without the additive (epsilon b similar to 16%), independent of M n. Near-optimal M g additives were effective at industrially relevant reaction times of 5-10 min, at loadings as low as 0.5 wt %, and in blends containing one of two different types of PET, suggesting their versatility and commercial applicability. Extensional viscosity was characterized and melt strain hardening (MSH) was observed to be highly dependent on the viscosity ratio between the matrix and dispersed phases, which is a function of temperature. When MSH is present, we show that reactive compatibilizers capable of forming branched reaction products offer an improvement to the MSH, compared to linear analogues. These findings suggest that branched compatibilizers may be advantageous for melt processability of compatibilized recyclates in processes dominated by strong extensional flows, such as film blowing, foaming, and thermoforming.

Hydroxy-telechelic polyalkenamers have long been synthesized using ring-opening metathesis polymerization (ROMP) in the presence of an acyclic olefin chain-transfer agent (CTA); however, this route typically requires protected diols in the CTA due to the challenge of alcohol-mediated degradation of ruthenium metathesis catalysts that can not only deactivate the catalysts, but also compromise the CTA. We demonstrate the synthesis and implementation of a new hydroxyl-containing CTA in which extended methylene spacers isolate the olefin and alcohol moieties to mitigate decomposition pathways. This CTA enabled the direct ROMP synthesis of hydroxy-telechelic polycyclooctene with controlled chain lengths dictated by the initial ratio of monomer to CTA. The elimination of protection/deprotection steps resulted in improved atom economy. Subsequent hydrogenation of the backbone olefins was performed by a one-pot, catalytic approach employing the ruthenium complex used for the initial ROMP. The resultant approach is a streamlined, atom-economic, and low-waste route to hydroxy-telechelic linear polyethylene that uses a green solvent, succeeds with miniscule quantities of catalyst (0.005 mol %), and requires no additional purification steps.

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.

Strong and well-engineered interfaces between dissimilar materials are a hallmark of natural systems but have proven difficult to emulate in synthetic materials, where interfaces often act as points of failure. In this work, curing reactions that are triggered by exposure to different wavelengths of visible light are used to produce multimaterial objects with tough, well-defined interfaces between chemically distinct domains. Longer-wavelength (green) light selectively initiates acrylate-based radical polymerization, while shorter-wavelength (blue) light results in the simultaneous formation of epoxy and acrylate networks through orthogonal cationic and radical processes. The improved mechanical strength of these interfaces is hypothesized to arise from a continuous acrylate network that bridges domains. Using printed test structures, interfaces were characterized through spatial resolution of their chemical composition, localized mechanical properties, and bulk fracture strength. This wavelength-selective photocuring of interpenetrating polymer networks is a promising strategy for increasing the mechanical performance of 3D-printed objects and expanding light-based additive manufacturing technologies.

As the scope of additive manufacturing broadens, interest has developed in 3D-printed objects that are derived from recyclable resins with chemical and mechanical tunability. Dynamic covalent bonds have the potential to not only increase the sustainability of 3D-printed objects, but also serve as reactive sites for postprinting derivatization. In this study, we use boronate esters as a key building block for the development of catalyst-free, 3D-printing resins with the ability to undergo room-temperature exchange at the cross-linking sites. The orthogonality of boronate esters is exploited in fast-curing, oxygen-tolerant thiol-ene resins in which the dynamic character of 3D-printed objects can be modulated by the addition of a static, covalent cross-linker with no room-temperature bond exchange. This allows the mechanical properties of printed parts to be varied between those of a traditional thermoset and a vitrimer. Objects printed with a hybrid dynamic/static resin exhibit a balance of structural stability (residual stress = 18%) and rapid exchange (characteristic relaxation time = 7 s), allowing for interfacial welding and postprinting functionalization. Modulation of the cross-linking density postprinting is enabled by selective hydrolysis of the boronate esters to generate networks with swelling capacities tunable from 1.3 to 3.3.

Facile, on-demand manufacturing of polymer foams with desirable properties such as mechanical strength, controlled porosity, and varied composition will enable the design of custom structural components for a variety of applications. A two-step process based on initial 3D photopolymerization and subsequent thermal processing is reported for creating thermally activated polymer foams with tunable pore size and volume fraction. The overall resin design incorporates photopolymerizable monomers (matrix) and thermally expandable microspheres (foaming agent) to produce microporosity throughout the resulting polymer network. During the microscopic expansion process, 3D printed polymeric parts irreversibly expand while retaining their overall shape. Low-density foams with a porosity up to 85% have been produced that exhibit increased specific modulus and energy dissipation when compared to the bulk matrix and unexpanded 3D printed parts. In addition, by tuning the cross-link density of the matrix network, it is possible to control pore size and material mechanics. This approach produces thermally activated polymer foams of complex geometries with programmed porosity and enhanced mechanical properties with the two-step process also providing local control over the spatial distribution of pore sizes through multimaterial 3D printing.

We introduce a design strategy to expand the range of accessible mechanical properties in covalent adaptable networks (CANs) using bottlebrush polymer building blocks. Well-defined bottlebrush polymers with rubbery poly(4-methylcaprolactone) side chains were cross-linked in formulations that include a bislactone and strong Lewis acid (tin ethylhexanoate). The resulting materials exhibit tunable stress-relaxation rates at elevated temperatures (160-180 degrees C) due to dynamic ester cross-links that undergo transesterification with residual hydroxy groups. Varying the cross-linker loading or bottlebrush backbone degree of polymerization yields predictable low-frequency shear moduli ca. 10-100 kPa, well below values typical of linear polymer CANs (1 MPa). These extensible networks can be stretched to strains as large as 350% before failure and undergo efficient self-healing to recover >85% of their original toughness upon repeated fracture and melt processing. In summary, molecular architecture creates new opportunities to tailor the mechanical properties of CANs in ways that are otherwise difficult to achieve.

Metal-free hydrosilylation using tris(pentafluorophenyl)borane (B(C6F5)3) as a catalyst enables the rapid polymerization of α-diketone and bis(silane) monomers under ambient conditions to give high molecular weight poly(silyl ether)s (PSEs). A wide selection of commercially available monomers bearing different backbone and side-chain functional groups are shown to be compatible with these metal-free conditions. Significantly, the thermal properties of these poly(silyl ether)s are highly tunable, with novel semicrystalline materials being obtained in a variety of cases. These poly(silyl ether) materials serve as a versatile platform for materials with designed degradation profiles and crystallinity.

Vulcanization of silicone networks from commercially available linear poly(dimethyl-co-methylhydro)siloxane (PMHS) and alpha-diketones was achieved using metal-free borane hydrosilylation at room temperature. The Lewis acid catalyst, tris(pentafluorophenyl)borane (B(C6F5)(3)), efficiently cross-linked PMHS at minimal catalyst loadings (200-1000 ppm) to produce polymer networks with mechanical properties, thermal stability, and optical clarity rivaling that achieved from traditional platinum catalysis. Variation of the starting PMHS structure is shown to influence the final characteristics of the network. Increasing molar mass of the PMHS chain results in a higher thermal decomposition temperature, while increasing mole fractions of Si-H moieties along the backbone increase the cross-linking density and the attendant Shore hardness. The degradation behavior of the networks was investigated, with the borane-vulcanized samples showing rapid dissolution upon exposure to acid and high stability to neutral and basic conditions. Functional networks bearing halide and vinyl groups could also be prepared via a preliminary reaction of PMHS with an appropriate monoketone, providing a general and versatile strategy for network derivatization with the potential for postvulcanization functionalization being subsequently demonstrated via thiol-ene click chemistry.

Modular synthesis of asymmetric rylenes from commercially available naphthalic anhydride derivatives provides access to novel materials with tunable functional handles at the imide-position, site-specific incorporation of bay position substituents and tailored extension of the molecular core.

Many insect wings change shape dynamically during the wingbeat cycle, and these deformations have the potential to confer energetic and aerodynamic benefits during flight. Due to the lack of musculature within the wing itself, the changing form of the wing is determined primarily by its passive response to inertial and aerodynamic forces. This response is in part controlled by the wing's mechanical properties, which vary across the membrane to produce regions of differing stiffness. Previous studies of wing mechanical properties have largely focused on surface or bulk measurements, but this ignores the layered nature of the wing. In our work, we investigated the mechanical properties of the wings of the house cricket (Acheta domesticus) with the aim of determining differences between layers within the wing. Nanoindentation was performed on both the surface and the interior layers of cross-sectioned samples of the wing to measure the Young's modulus and hardness of the outer- and innermost layers. The results demonstrate that the interior of the wing is stiffer than the surface, and both properties vary across the wing.