TY - JOUR
T1 - Functional Upcycling of Polyurethane Thermosets into Value-Added Thermoplastics via Small-Molecule Carbamate-Assisted Decross-Linking Extrusion
AU - Nettles, Jared A.
AU - Alfarhan, Saleh
AU - Pascoe, Cameron A.
AU - Westover, Clarissa
AU - Madsen, Margaret D.
AU - Sintas, Jose I.
AU - Subbiah, Aadhi
AU - Long, Timothy E.
AU - Jin, Kailong
N1 - Publisher Copyright:
© 2024 The Authors. Published by American Chemical Society.
PY - 2024/8/26
Y1 - 2024/8/26
N2 - The cross-linked structures of most commodity polyurethanes (PUs) hinder their recycling by common mechanical/chemical approaches. Catalyzed dynamic carbamate exchange emerges as a promising PU recycling strategy, which converts traditional static PU thermosets into reprocessable covalent adaptable networks (CANs). However, this approach has been limited to thermoset-to-thermoset reprocessing of PU CANs, accompanied by their well-preserved network structures and extremely high viscosities, which pose challenges to processing and certain applications. This study reports a catalytic decross-linking extrusion process aided by small-molecule carbamates, which can upcycle PU thermosets into easily processable and functional PU thermoplastics in a solvent-free and high-throughput manner. Key to this process is the employment of small-molecule carbamates as decross-linkers to simultaneously deconstruct cross-linked PUs and functionalize the decross-linked PU chains, through catalyzed carbamate exchange reactions in a twin-screw extruder. This strategy applies to both aromatic and aliphatic cross-linked PU films and foams, and the amount of small-molecule carbamates required to decross-link PU networks is determined through thermal, chemical, and structural analyses of the resulting extrudates. This approach is generalizable to small-molecule carbamates with various steric/electronic structures and chemical functionalities including methacrylate, anthracene, and stilbene groups. The chain-end functionalization is confirmed by analyzing the purified decross-linked extrudates after dialysis. This thermoset-to-thermoplastic extrusion process represents a powerful approach for upcycling postconsumer PU thermosets into a library of thermoplastic PUs with controlled molecular weights and chain-end functionalities for diverse applications, including adhesives, photoresins, and stimuli-responsive materials, as demonstrated herein. In the future, this strategy could be extended to upcycle many other step-growth networks capable of undergoing catalytic bond exchange reactions, such as cross-linked polyureas and polyesters, contributing to plastic waste management in general.
AB - The cross-linked structures of most commodity polyurethanes (PUs) hinder their recycling by common mechanical/chemical approaches. Catalyzed dynamic carbamate exchange emerges as a promising PU recycling strategy, which converts traditional static PU thermosets into reprocessable covalent adaptable networks (CANs). However, this approach has been limited to thermoset-to-thermoset reprocessing of PU CANs, accompanied by their well-preserved network structures and extremely high viscosities, which pose challenges to processing and certain applications. This study reports a catalytic decross-linking extrusion process aided by small-molecule carbamates, which can upcycle PU thermosets into easily processable and functional PU thermoplastics in a solvent-free and high-throughput manner. Key to this process is the employment of small-molecule carbamates as decross-linkers to simultaneously deconstruct cross-linked PUs and functionalize the decross-linked PU chains, through catalyzed carbamate exchange reactions in a twin-screw extruder. This strategy applies to both aromatic and aliphatic cross-linked PU films and foams, and the amount of small-molecule carbamates required to decross-link PU networks is determined through thermal, chemical, and structural analyses of the resulting extrudates. This approach is generalizable to small-molecule carbamates with various steric/electronic structures and chemical functionalities including methacrylate, anthracene, and stilbene groups. The chain-end functionalization is confirmed by analyzing the purified decross-linked extrudates after dialysis. This thermoset-to-thermoplastic extrusion process represents a powerful approach for upcycling postconsumer PU thermosets into a library of thermoplastic PUs with controlled molecular weights and chain-end functionalities for diverse applications, including adhesives, photoresins, and stimuli-responsive materials, as demonstrated herein. In the future, this strategy could be extended to upcycle many other step-growth networks capable of undergoing catalytic bond exchange reactions, such as cross-linked polyureas and polyesters, contributing to plastic waste management in general.
KW - carbamate bond exchange
KW - covalent adaptable networks
KW - cross-linked polyurethane
KW - plastic recycling
KW - polyurethane depolymerization
KW - reactive extrusion
KW - sustainability
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U2 - 10.1021/jacsau.4c00403
DO - 10.1021/jacsau.4c00403
M3 - Article
AN - SCOPUS:85198568194
SN - 2691-3704
VL - 4
SP - 3058
EP - 3069
JO - JACS Au
JF - JACS Au
IS - 8
ER -