Kinetically and Thermodynamically Controlled Cross-Linking in Sustainable Digital Light Processing Printing: Enabling Thermoset Reprocessing via Thermal Leveling Effect

Kinetically and Thermodynamically Controlled Cross-Linking in Sustainable Digital Light Processing Printing: Enabling Thermoset Reprocessing via Thermal Leveling Effect

ACS Materials Letters

10.1021/acsmaterialslett.4c02465

https://doi.org/10.1021/acsmaterialslett.4c02465

Yi Ting Chong, Suxi Wang, Sirawit Pruksawan, Zhuang Mao Png, Qiang Zhu, Zibiao Li, Fuke Wang

21 April 2025

Chong, Y. T., Wang, S., Pruksawan, S., Png, Z. M., Zhu, Q., Li, Z., & Wang, F. (2025). Kinetically and Thermodynamically Controlled Cross-Linking in Sustainable Digital Light Processing Printing: Enabling Thermoset Reprocessing via Thermal Leveling Effect. ACS Materials Letters, 7(5), 1963–1972. https://doi.org/10.1021/acsmaterialslett.4c02465

High-performance resins are essential for DLP 3D printing, yet most are thermosetting and lack re-processability. Recently developed covalent adaptive networks (CANs) address this limitation but its reliance on specialized monomers hinders scalability and practical application. Herein, we report a 3D-printable resin formulated with isobornyl acrylate, a 1,2-diol-based boronic ester cross-linker (<4%), and tetradecanol as a trans-borylesterification mediator. At room temperature, tetradecanol remains unreactive, preserving a rigid thermoset matrix while forming micro-elastic domains that dissipate impact energy, achieving an 8600% increase in toughness with 15% tetradecanol. During hot pressing, the thermal levelling effect kinetically drives dynamic bond exchange, converting the thermoset into thermoplastic material. Upon cooling, the reaction becomes thermodynamically controlled again, reestablishing the thermoset polymer network and recovering mechanical properties. This resin uniquely transitions to a thermoplastic state only during reprocessing, reverting to a durable thermoset upon cooling, enabling sustainable, high-performance DLP printing with end-of-life reusability.

Publisher Copyright

This research / project is supported by the A*STAR - RIE2025 Manufacturing, Trade and Connectivity (MTC) Programmatic Fund
Grant Reference no. : M22K9b0049

This research / project is supported by the A*STAR - RIE2025 Manufacturing, Trade and Connectivity (MTC) Programmatic Fund
Grant Reference no. : M24N3b0028

This research / project is supported by the A*STAR - SERC Central Research Fund (TIMR211001bSERCRF)
Grant Reference no. : TIMR211001bSERCRF

This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Materials Letters, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acsmaterialslett.4c02465 .

https://oar.a-star.edu.sg/communities-collections/articles/23147

2639-4979
2639-4979

Institute of Materials Research and Engineering