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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.

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.

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.

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.

This is the final report from a NSF-sponsored Square Table on Sustainable Polymers that brought together a diverse cohort of stakeholders to develop broad-ranging, integrated, and futuristic ideas and strategies in the area of sustainable polymers. The Square Table included emerging and established leaders from a wide range of backgrounds and institutional types such that a clear picture of the key challenges and needs were developed. Over the course of two half-day sessions, a group of more than 50 participants (see Appendix 1) discussed strategies for advancing the science, technology, and more overarching systems associated with sustainable polymers. The Square Table concept provides structure and self-facilitated interactions among stakeholders who do not typically interact with one another to bridge gaps that exist between industry, federal agencies, and academia in an open and unbiased manner. This was accomplished by mixing participants in breakout discussion with guiding questions, followed by reporting back to the group and repeating with a new mix of participants, questions, and discussion points. Select participants that not only contributed to the discussion but also acted as scribes for sub-sessions were essential to help capture the sum of the views, suggestions, and inputs from the participants. In this way, the discussions cut to the root cause of successes and opportunities in a rapid and less biased manner than traditional roundtables or workshops. The Square Table objectives included developing proposed answers to key questions such as (1) What are the critical basic and applied questions that, when addressed together, could improve the possibility for impact in terms of moving fundamental research thrusts and translational efforts? (2) What prevents large-scale, coordinated efforts between industry, academia, and federal agencies? (3) What is needed to help reduce these barriers in terms of data resources, physical infrastructure, and/or workforce training? (4) How can data and advanced modeling approaches be shared in a collaborative way that would allow data-driven science and engineering to be accelerated in a translational sense? (5) What partnerships are needed to foster an environment/culture to realize more sustainable polymer solutions in the future?

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.

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 °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.

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.

The modular synthesis of asymmetric rylenes from naphthalic anhydride derivatives is presented. Imidization, Suzuki–Miyaura coupling and cyclodehydrogenation reactions are utilized for the generation of novel functional rylenes with these three core transformations providing significant flexibility over the final structure. The combination of simple purification and high yields enables access to asymmetric rylenes with functional handles at the imide-position and site-specific incorporation of bay position substituents. The resulting library of perylenes and bisnapthalimide-anthracene derivatives showcase the presented methodology and the ability to tune optoelectronic and electrochemical properties.

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., Massachusetts Institute of Technology. Department of Materials Science and Engineering

We report that the interlayer diffusion of polymer chains within heterostructured hydrogen-bonded multilayer films depends on the stacking order: polymers diffuse more when high pH stability polymer pairs are assembled on top of low pH stability polymer pairs. By varying the stacking sequence, the fraction of the film that is released from the substrate can be tuned to achieve sequential pH-programmed release of the multilayer film. Also, we show that a multifunctional freestanding film with tunable film thickness can be generated by appropriate stacking and subsequent thermal cross-linking.

International audience; We report experimental results on the propagation of ultrasonic waves (at frequencies in the range of 40 kHz) in aqueous foams. Monitoring the acoustics of the foams as they age, i.e. as the mean bubble radius increases by coarsening, we recover at short times some trends that are already known: decrease of the speed of sound and increase of attenuation. At long times, we have identified, for the first time, robust non-monotonic behaviors of the speed of sound and attenuation, associated with a critical bubble size, which decreases at increasing frequency. The experimental features appear to be surprisingly reminiscent of the Minnaert resonance known for a single isolated bubble in a fluid. Transposing the Minnaert theoretical framework to the limit of a dense packing of bubbles gives some qualitative agreement with the data, but still cannot explain quantitatively the measured properties.

Sound propagation through liquid foams, which are dispersions of gas bubbles in a continuous liquid phase, is not well known yet. To characterize foam acoustics at the local scale, we have studied the effect of an external acoustic wave on bubble displacements inside an aqueous foam. We quantify these displacements by using a technique based on optical diffusive wave spectroscopy, that we specially developped to resolve tiny deformations in materials. Bubble displacements induce a modulation on the photon correlation curve. Measurements for various sound frequencies and amplitudes are interpreted using a light diffusion model. It allows us to unravel a nontrivial acoustic displacement profile inside the foam; in particular, we find that the acoustic wave creates a localized shear in the vicinity of the solid walls holding the foam, as a consequence of inertial contributions. This study of how bubbles "dance" inside a foam as a response to sound turns out to provide new insights on foam acoustics and sound transmission into a foam, foam deformation at high frequencies, and analysis of light scattering data in samples undergoing nonhomogeneous deformations.