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Effects of cleavable comonomer structure and crosslinker chemistry on the performance and deconstructability of frontally cured pDCPD composites

Reclaiming undamaged carbon fiber from thermoset composites requires chemical recycling methods that leverage complete deconstruction of the polymer matrix. Cleavable comonomers enable chemical recycling of poly(dicyclopentadiene) (pDCPD) composites, but current systems suffer from reduced glass transition temperature (T g ), limiting application. Here, we investigate the effect of cleavable comonomer loading and cleavable crosslinker chemistry on network formation, thermomechanical properties, and fiber recovery in frontally cured pDCPD composites. All formulations fully deconstructed in acid and recovered fibers ranged from pristine to variably contaminated depending on crosslinker chemistry. Reducing backbone-cleaving comonomer content and introducing cleavable crosslinkers raised composite T g to 126–138 °C compared to 105 °C previously reported in deconstructable pDCPD composites. Although the cleavable crosslinkers increased T g in unreinforced polymers to 150–160 °C, the fiber-reinforced composite T g remained lower due to under-curing and interactions between the crosslinkers and the fiber surface. Increasing polymerization initiator loading improved comonomer conversion and yielded a deconstructable composite with T g = 151 °C, approaching the performance of non-deconstructable pDCPD composites (T g = 161 °C). This work clarifies how cleavable comonomer and crosslinker chemistry governs curing, thermomechanical performance, and reclaimed reinforcement quality, and the results highlight the need for more robust cleavable comonomers to realize multigenerational composite materials without sacrificing thermomechanical performance.

Carbon fibers

Simulation-driven design optimization of reaction injection molding (RIM) process for polydicyclopentadiene (pDCPD): Minimizing cycle time, defects, and warpage

Replacing metal components in trucks, trailers, and buses with lightweight polymer composites is challenging due to high temperatures and complex manufacturing. The Reaction Injection Molding (RIM) process using Dicyclopentadiene (DCPD) resin offers a solution by producing robust parts with excellent stiffness, impact strength, and resistance properties. Simulations are essential for optimizing this process, predicting defects, and improving quality. However, most commercial software is tailored for thermoplastics, requiring thermoset users to generate their own datasets. In this study, a material data card for DCPD was developed to perform RIM simulations. Design of Experiments (DOE) was used to identify key factors affecting filling, curing, and warpage, aiming to minimize cycle time and defects. The simulations explored varying injection gate parameters (size, location, number) and process conditions (mold/resin temperature, injection/curing pressure). Results showed that gate design significantly impacts filling behavior and defects. A single central gate provided balanced flow with fewer defects, while two corner gates led to more defects. Additionally, lower injection pressure increased filling time, while higher mold temperature accelerated curing but led to more warpage. In conclusion, this optimization framework aims to enhance DCPD part performance and promote sustainable manufacturing by reducing waste and energy consumption.

42 ENGINEERING

Effects of a Small Fraction of Norbornene Comonomers on the Frontal Ring Opening Metathesis Polymerization of Dicyclopentadiene and Dihydrofuran

Frontal ring-opening metathesis polymerization (FROMP) is an energy-efficient process for the construction of high performance polydicyclopentadiene (pDCPD) thermosets. A small fraction of norbornene (NBE) comonomer is often added to DCPD to liquify the resin, but their effects on the resin chemistry and frontal curing characteristics are not quantitatively understood, especially for recently developed deconstructable DCPD resins containing cleavable comonomers. 2,3-Dihydrofuran (DHF) is a commercially available, effective cleavable comonomer for ROMP of norbornenes, and it has been recently demonstrated to enable full deconstruction of pDCPD thermosets at 5% loading. Herein, we investigated deconstructable DCPD resins containing 5% of different (oxa)NBE derivatives and 5% DHF. We report the effects of such a small fraction of (oxa)NBE comonomers on the resin pot life (room temperature resin reactivity), front curing characteristics, degree of cure, crosslinking density, comonomer distribution, and deconstruction kinetics of the resulting pDCPD thermosets. These effects can be correlated to the metathesis reactivity of these comonomers. As a result, this study provides quantitative understanding that will guide the future development of new deconstructable FROMP resins with desired construction and deconstruction characteristics.

Luo, Xuyi [Stanford University, CA (United States)

Upcycling Polynorbornene Derivatives into Chemically Recyclable Multiblock Linear and Thermoset Plastics

Synthetic polymers have found widespread use, but their ineffective end-of-life treatment is causing a significant environmental and human health crisis. Here, we demonstrate the upcycling of polynorbornene derivatives (pNBEs) through their deconstruction into distinct oligomeric buildings blocks that can be repolymerized into chemically recyclable pNBEs-like multiblock polymers via dehydrogenative polymerization. The resulting materials exhibit diverse mechanical properties, while integrating high melting temperatures (T m as high as 133 °C). Notably, this method could also enable the selective deconstruction of permanently cross-linked polydicyclopentadiene (pDCPD) thermosets into telechelic-OH functionalized oligomers, overcoming the significant challenges posed by their robust network structure in recycling and degradation. The resulting pDCPD oligomers can subsequently be repolymerized with macrodiols to create multiblock thermosets with tunable mechanical properties, including Young's modulus and tensile elongation. After use, upcycled plastics could be effectively deconstructed back to the oligomers for recovery and repolymerization. Overall, this work establishes an approach that can be utilized to upcycle pNBEs into previously inaccessible multiblock thermosets and thermoplastics with full recyclability, and may be generalizable to a range of polymers to shift their end-of-life waste disposal toward sustainable recovery and reuse.

36 MATERIALS SCIENCE

Cleavable Strand‐Fusing Cross‐Linkers as Additives for Chemically Deconstructable Thermosets with Preserved Thermomechanical Properties

Abstract Permanently cross‐linked polymer networks—thermosets—are often difficult to chemically deconstruct. The installation of cleavable bonds into the strands of thermosets using cleavable comonomers as additives can facilitate thermoset deconstruction without replacement of permanent cross‐links, but such monomers can lead to reduced thermomechanical properties and require high loadings to function effectively, motivating the design of new and optimal cleavable additives. Here, we introduce “strand‐fusing cross‐linkers” (SFCs), which fuse two network strands via a four‐way cleavable cross‐link. SFCs enable deconstruction of model polydicyclopentadiene (pDCPD) thermosets with as little as one‐fifth of the molar loading needed to achieve deconstruction using traditional cleavable comonomers. SFCs function under traditional oven curing as well as low‐energy frontal ring‐opening metathesis polymerization (FROMP) conditions and lead to improved thermomechanical properties, for example, glass transition temperatures, compared to prior cleavable comonomer designs. This work motivates the development of increasingly improved cleavable additives to enable thermoset deconstruction without compromising material performance.

Zhang, Shuyi [Department of Chemistry Massachusett

Cleavable Strand‐Fusing Cross‐Linkers as Additives for Chemically Deconstructable Thermosets with Preserved Thermomechanical Properties

Abstract Permanently cross‐linked polymer networks—thermosets—are often difficult to chemically deconstruct. The installation of cleavable bonds into the strands of thermosets using cleavable comonomers as additives can facilitate thermoset deconstruction without replacement of permanent cross‐links, but such monomers can lead to reduced thermomechanical properties and require high loadings to function effectively, motivating the design of new and optimal cleavable additives. Here, we introduce “strand‐fusing cross‐linkers” (SFCs), which fuse two network strands via a four‐way cleavable cross‐link. SFCs enable deconstruction of model polydicyclopentadiene (pDCPD) thermosets with as little as one‐fifth of the molar loading needed to achieve deconstruction using traditional cleavable comonomers. SFCs function under traditional oven curing as well as low‐energy frontal ring‐opening metathesis polymerization (FROMP) conditions and lead to improved thermomechanical properties, for example, glass transition temperatures, compared to prior cleavable comonomer designs. This work motivates the development of increasingly improved cleavable additives to enable thermoset deconstruction without compromising material performance.

Zhang, Shuyi [Department of Chemistry Massachusett