Vitrimers form a promising class of dynamic polymer networks, but they have an Achilles’ heel: elastomeric vitrimers exhibit significant creep under conditions where permanently cross-linked, elastomeric networks exhibit little or no creep. We demonstrate that vitrimers can be designed with strongly suppressed creep and excellent reprocessability by incorporating a substantial yet subcritical fraction of permanent cross-links. This critical fraction of permanent cross-links, which has little or no detrimental effect on reprocessability, is defined by the gelation point of only permanent cross-links leading to a percolated permanent network. Via a modification of classic Flory–Stockmayer theory, we have developed a simple theory that quantitatively predicts an approximate limiting fraction. To test our theory, we designed vitrimers with controlled fractions of permanent cross-links based on thiol–epoxy click chemistry. We characterized the rubbery plateau modulus before and after reprocessing as well as stress relaxation of our original vitrimers. Our experimental results strongly support our theoretical prediction: as long as the fraction of permanent cross-links is insufficient to form a percolated permanent network, the vitrimer can be reprocessed with full recovery of cross-link density. In particular, with a predicted limiting fraction of 50 mol %, a vitrimer system designed with 40 mol % permanent cross-links achieved full property recovery associated with cross-link density after reprocessing as well as 65–71% creep reduction (for both original and reprocessed samples) relative to a similar vitrimer without permanent cross-links. In contrast, a system with 60 mol % permanent cross-links could not be reprocessed into a well-consolidated sample, nor did it recover full cross-link density; it failed by breaking at early stages of creep tests. The ability to predict an approximate limiting fraction of permanent cross-links leading to enhanced creep resistance and full reprocessability represents an important advance in the science and design of vitrimers.

We developed reprocessable polyhydroxyurethane (PHU) networks with full property recovery and incorporating both associative and dissociative dynamic chemistry.

A series of isotactic polypropylene (iPP) and polyethylene (PE) diblock, tetrablock, and hexablock copolymers (BCPs) were synthesized with tunable molecular weights using a hafnium pyridylamine catalyst. The BCPs were melt blended with 70 wt % high-density PE (HDPE) and 30 wt % iPP commercial homopolymers at concentrations between 0.2 and 5 wt %. The resulting blend morphologies were investigated using TEM, revealing uniformly dispersed iPP droplets ranging progressively in size with increasing BCP content from three-quarters to one-quarter of the diameter of the uncompatibilized mixture. Tensile tests revealed a dramatic enhancement in toughness based on the strain at break which increased from 10% for the unmodified blend to more than 300% with just 0.2 wt % BCP and over 500% with the addition of 0.5 wt % BCP or greater. Incorporation of BCPs in blends also improved the impact toughness, doubling the Izod impact strength to a level comparable to the neat HDPE with just 1 wt % additive. These improved blend properties are attributed to enhanced interfacial strength, which was independently probed using T-peel adhesion measurements performed on laminates composed of HDPE/BCP/iPP trilayers. Thin (ca. ≤100 nm thick) BCP films, fabricated by high-temperature spin coating and molded between the homopolymer films, significantly altered the laminate peel strength, depending on the molecular weight and molecular architecture of the block copolymer. Multilayer laminates containing no BCP or low molecular weight diblock copolymer separated by adhesive failure during peel testing. Sufficiently high molecular weight iPP–PE diblock copolymers and iPP–PE–iPP–PE tetrablock copolymers with significantly lower block molecular weights exhibited cohesive failure of the HDPE film rather than adhesive failure. We propose adhesion mechanisms based on molecular entanglements and cocrystallization for tetrablocks and diblocks, respectively, to account for these findings. These results demonstrate exciting opportunities to recycle the world’s top two polymers through simple melt blending, obviating the need to separate these plastics in mixed waste streams.

A nitroxide-mediated polymerization strategy allows one-step synthesis of recyclable crosslinked polymeric materials from any monomers or polymers that contain carbon-carbon double bonds amenable to radical polymerization. The resulting materials with dynamic covalent bonds can show full property recovery after multiple melt-reprocessing recycles. This one-step strategy provides for both robust, relatively sustainable recyclability of crosslinked polymers and design of networks for advanced technologies.

Cross-linked polyurethane (PU) is extensively used as thermoset foam; however, methods to directly reprocess PU foam waste derived from commercial sources into similar value materials have not been developed. We demonstrate that introducing dibutyltin dilaurate (DBTDL) into cross-linked PU foams and films enables their reprocessing at elevated temperatures via dynamic carbamate exchange reactions. Both model and commercial cross-linked PU foams were continuously reprocessed using twin-screw extrusion to remove gaseous filler and produce PU filaments or films with elastomeric or rigid thermoset mechanical properties. The properties of microcompounded model PU foam were in excellent agreement with PU film synthesized using the same monomers, indicating that this process occurs efficiently. These findings will enable the bulk reprocessing of commercial thermoset PU waste and inspire the further development of reprocessing methods for other thermosets and the compatibilization of chemically distinct cross-linked materials.