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.
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.
Metal-free hydrosilylation using tris-(pentafluorophenyl)borane (B(C 6 F 5 ) 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.
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.
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.
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