Many common polymers, especially vinyl are inherently difficult to chemically recycle and environmentally persistent. The introduction of low levels cleavable comonomer additives into existing polymerization processes could facilitate the production deconstructable recyclable variants with otherwise equivalent properties. Here, we report thionolactones that serve as for chemical deconstruction recycling polymers prepared through free radical polymerization, using polystyrene (PS) a model...

Convenient strategies for the deconstruction and reprocessing of thermosets could improve circularity these materials, but most approaches developed to date do not involve established, high-performance engineering materials. Here, we show that bifunctional silyl ether, i.e., R'O-SiR2-OR'', (BSE)-based comonomers generate covalent adaptable network analogues industrial thermoset polydicyclopentadiene (pDCPD) through a novel BSE exchange process facilitated by low-cost food-safe catalyst...

Thermosets present sustainability challenges that could potentially be addressed through the design of deconstructable variants with tunable properties; however, combinatorial space possible thermoset molecular building blocks (e.g., monomers, cross-linkers, and additives) manufacturing conditions is vast, predictive knowledge for how combinations these components translate to bulk properties lacking. Data science overcome problems, but computational methods are difficult apply...

"Drop-in" additives that introduce chemically cleavable bonds into thermosets without compromising thermomechanical properties could enable triggered material deconstruction and enhanced sustainability. While the installation of strands commercial thermoset polydicyclopentadiene (pDCPD) using comonomers facilitates chemical deconstruction, these can lower material's glass transition temperature (Tg). By contrast, crosslinkers pDCPD maintain or potentially increase Tg but does not facilitate...

The synthesis of novel polysilylethers via entropy-driven ring-opening metathesis polymerization (ED-ROMP) cyclic bifunctional silyl ether-based monomers is reported. These polymers display good thermal stability and ultra-low Tg (-88 °C). Moreover, they are rapidly deconstructable the cleavage silicon-oxygen linkages with acid or fluoride triggers, were partially depolymerizable by addition exogenous catalyst. Analysis deconstructed polymer products provided insight into microstructure,...

Thermoset polymers and fiber-reinforced polymer composites possess the chemical, physical, mechanical properties necessary for energy-efficient vehicles structures, but their energy-inefficient manufacturing lack of end-of-life management strategies render these materials unsustainable. Here, we demonstrate deconstruction upcycling high-performance poly(dicyclopentadiene) (pDCPD) thermosets with a concurrent reduction in energy demand curing via frontal copolymerization. Triggered material...

Permanently cross-linked polymer networks-thermosets-are often difficult to chemically deconstruct. The installation of cleavable bonds into the strands thermosets using comonomers as additives can facilitate thermoset deconstruction without replacement permanent cross-links, but such monomers lead reduced thermomechanical properties and require high loadings function effectively, motivating design new optimal additives. Here, we introduce "strand-fusing cross-linkers" (SFCs), which fuse two...

Abstract Permanently cross‐linked polymer networks—thermosets—are often difficult to chemically deconstruct. The installation of cleavable bonds into the strands thermosets using comonomers as additives can facilitate thermoset deconstruction without replacement permanent cross‐links, but such monomers lead reduced thermomechanical properties and require high loadings function effectively, motivating design new optimal additives. Here, we introduce “strand‐fusing cross‐linkers” (SFCs), which...

Conducting polymer fabricated oil-in-water (o/w) colloidal particles were developed via a single step of in situ interfacial polymerization an emulsion phase, exhibiting unique core–shell structure, where the shell was governed by thin layer polypyrrole (pPy) film at o/w interface. These afford dynamic actuating shapes and configurations when pPy interface is chemically oxidized into charged state or, alternatively, it reduced noncharged state. Mechanisms particles' volumetric expansion rely...

While Si-containing polymers can often be deconstructed using chemical triggers such as fluoride, acids, and bases, they are resistant to cleavage by mild reagents biological nucleophiles, thus limiting their end-of-life options potential environmental degradability. Here, ring-opening metathesis polymerization, we synthesize terpolymers of (1) a "functional" monomer (e.g., polyethylene glycol macromonomer or dicyclopentadiene); (2) containing an electrophilic pentafluorophenyl (PFP)...

Graft copolymers offer a versatile platform for the design of self-assembling materials; however, simple strategies precisely and independently controlling thermomechanical morphological properties graft remain elusive. Here, using library 92 polynorbornene-graft-polydimethylsiloxane (PDMS) copolymers, we discover backbone-pendant sequence-control strategy that addresses this challenge. Small structural variations pendant groups, e.g., cyclohexyl versus n-hexyl, small-molecule comonomers...

Abstract Thermoset toughness and deconstructability are often opposing features; simultaneously improving both without sacrificing other mechanical properties (e.g., stiffness tensile strength) is difficult, but, if achieved, could enhance the usage lifetime end‐of‐life options for these materials. Here, a strategy that addresses this challenge in context of photopolymer resins commonly used 3D printing glassy, acrylic thermosets introduced. It shown incorporating bis‐acrylate...

Thermosets play a key role in the modern plastics and rubber industries, comprising ~18% of polymeric materials with worldwide annual production 65 million tons. The high density crosslinks that give these their useful properties comes at expense facile degradability re/upcyclability. Here, using high-performance industrial thermoset plastic poly-dicyclopentadiene (pDCPD) as model system, we show when small number cleavable bonds are selectively installed within strands low-cost comonomer...

Abstract Graft copolymers offer a versatile platform for the design of self-assembling materials; however, simple strategies precisely and independently controlling thermomechanical morphological properties graft over wide property windows remain elusive. Here, using library 92 systematically varied polynorbornene-graft-polydimethylsiloxane (PDMS) copolymers, we discover backbone-pendant sequence control strategy that overcomes this challenge. We find small structural variations aliphatic...

Thermoset polymers and fiber-reinforced polymer composites possess the chemical, physical, mechanical properties necessary for energy-efficient vehicles structures, but their energy-inefficient manufacturing lack of end-of-life strategies render these materials unsustainable. Here, we demonstrate deconstruction upcycling high-performance poly(dicyclopentadiene) (pDCPD) thermosets with a concurrent reduction in energy demand curing via frontal copolymerization. Triggered material is achieved...

Data science can accelerate materials discovery by learning composition-processing-performance models from pre-existing data sets, which then feed into active cycles in the laboratory. Thermoset polymer waste is a pressing environmental challenge that may be addressed accelerated of new deconstructable variants; however, combinatorial space possible monomers, crosslinkers, additives, and manufacturing conditions vast Edisonian experimentation struggle to find optimal designs. Moreover,...

Fiber-reinforced thermoset polymer matrix composites (FRPCs) possess the chemical, physical, and mechanical properties required for applications in critical industries such as defense, transportation, energy. However, FRPCs lack sustainable end-of-life management strategies that recapture their desirable thermomechanical properties. Frontal curing with cleavable comonomers is a promising strategy to extend lifecycle of constituent materials used by decreasing manufacturing cost improving...

Thermosets play a key role in the modern plastics and rubber industries, comprising ~18% of polymeric materials with worldwide annual production 65 million tons. The high density crosslinks that give these their useful properties comes at expense facile degradability re/upcyclability. Here, using high-performance industrial thermoset plastic poly-dicyclopentadiene (pDCPD) as model system, we show when small number cleavable bonds are selectively installed within strands low-cost comonomer...

Thermoset polymers and fiber-reinforced polymer composites possess the chemical, physical, mechanical properties necessary for energy-efficient vehicles structures, but their energy-inefficient manufacturing lack of end-of-life strategies render these materials unsustainable. Here, we demonstrate deconstruction upcycling high-performance poly(dicyclopentadiene) (pDCPD) thermosets with a concurrent reduction in energy demand curing via frontal copolymerization. Triggered material is achieved...