Mechanically Robust, Self-Healing, and Reprocessable Geraniol Based Epoxy Vitrimer by Dynamic Boronic Ester Bonds
Category
Sciences and Technology
Department
Polymer Chemistry
Student Status
Graduate
Research Advisor
Dr. Ram K. Gupta
Document Type
Event
Location
Governors
Start Date
10-4-2025 8:50 AM
End Date
10-4-2025 9:10 AM
Description
Covalent Adaptable Networks (CANs) are an emerging class of polymers with reversible covalent crosslinks that respond dynamically to external stimuli. Unlike conventional thermosets, CANs-particularly vitrimers- exhibit self-healing, reprocessability, shape memory, and recyclability due to their adaptable crosslinking chemistry. The widespread use of thermosets has led to growing concerns over the depletion of petroleum-based resources and environmental impact. To address these challenges, bio-based alternatives offer a sustainable pathway for developing high-performance materials. Geraniol, a naturally occurring monoterpenoid alcohol found in various plant oils, serves as a promising renewable feedstock for polymer synthesis. This study presents the first development of a geraniol-based epoxy vitrimer synthesized via a thermally activated thiol-epoxy click reaction between a geraniol-derived epoxy resin and a diboronic ester dithiol (DBDT) cross-linker. The incorporation of dynamic boronic ester bonds facilitates topological rearrangements, enabling efficient self-healing and reprocessability. The vitrimer demonstrates excellent thermal stability and mechanical strength, with a glass transition temperature (Tg) of 38.43℃ determined through Dynamic Mechanical Analysis (DMA). Additionally, it exhibits a tensile strength of approximately 19 MPa, shape memory behavior, solvent-based recyclability, and outstanding mechanical strength retention after reprocessing. The vitrimer also features a rapid relaxation time of 9 seconds at 140C and an activation energy of 22.44 kJ/mol, highlighting its efficient bond exchange capability. These attributes make the developed vitrimer a strong candidate for sustainable, high-performance applications, offering a viable alternative to traditional thermosets with enhanced environmental benefits.
Mechanically Robust, Self-Healing, and Reprocessable Geraniol Based Epoxy Vitrimer by Dynamic Boronic Ester Bonds
Governors
Covalent Adaptable Networks (CANs) are an emerging class of polymers with reversible covalent crosslinks that respond dynamically to external stimuli. Unlike conventional thermosets, CANs-particularly vitrimers- exhibit self-healing, reprocessability, shape memory, and recyclability due to their adaptable crosslinking chemistry. The widespread use of thermosets has led to growing concerns over the depletion of petroleum-based resources and environmental impact. To address these challenges, bio-based alternatives offer a sustainable pathway for developing high-performance materials. Geraniol, a naturally occurring monoterpenoid alcohol found in various plant oils, serves as a promising renewable feedstock for polymer synthesis. This study presents the first development of a geraniol-based epoxy vitrimer synthesized via a thermally activated thiol-epoxy click reaction between a geraniol-derived epoxy resin and a diboronic ester dithiol (DBDT) cross-linker. The incorporation of dynamic boronic ester bonds facilitates topological rearrangements, enabling efficient self-healing and reprocessability. The vitrimer demonstrates excellent thermal stability and mechanical strength, with a glass transition temperature (Tg) of 38.43℃ determined through Dynamic Mechanical Analysis (DMA). Additionally, it exhibits a tensile strength of approximately 19 MPa, shape memory behavior, solvent-based recyclability, and outstanding mechanical strength retention after reprocessing. The vitrimer also features a rapid relaxation time of 9 seconds at 140C and an activation energy of 22.44 kJ/mol, highlighting its efficient bond exchange capability. These attributes make the developed vitrimer a strong candidate for sustainable, high-performance applications, offering a viable alternative to traditional thermosets with enhanced environmental benefits.
