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0 26060207 - 26060207

DOI: https://doi.org/10.6023/A26060207

Article

The Latent Curing and Highly Efficient Degrading Epoxy System based on B-N Coordination

  • 孙晓冉 ,
  • 刘子宇 ,
  • 刘敬楷 ,
  • 刘小青
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  • Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201

Received date: 2026-06-19

  Online published: 2026-08-25

Supported by

Project funded by the National Natural Science Foundation of China (U23A20589).

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Abstract

In this study, the bifunctional phenylboronic ester (BACT) was synthesized via a dehydrative condensation reaction between 1,4-benzenediboronic acid and catechol. Subsequently, a thermally reversible B-N coordinated complex (B-M) was prepared through the coordination of BACT with 4-methoxypyridine, which was then employed as a latent curing accelerator for the one-component epoxy/anhydride system (E-51/MTHPA). This molecular design strategically imparts two pivotal functionalities to the formulated resin: exceptional storage stability at room temperature (25 ℃) and markedly enhanced degradability of the crosslinked thermoset network upon exposure to alkaline conditions. Specifically, at ambient temperature, the lone-pair electrons of the pyridinic N coordinate with the vacant p-orbital of the B, forming a dative B-N bond that effectively sequesters the nucleophilic catalytic activity of the pyridine moiety. This coordination temporarily suppresses its ability to initiate the epoxy/anhydride system curing reaction, thereby ensuring prolonged storage life. Upon heating to medium-high temperatures (exceeding 60 ℃), the reversible B-N dative bond undergoes thermally induced dissociation, regenerating the active 4-methoxypyridine species to efficiently promote the curing reaction. Concurrently, beyond its role as a reversible protecting group for the catalyst, the BACT actively participates in the curing process with the epoxy/anhydride system, resulting in the covalent incorporation of more easily hydrolyzable borate ester linkages into the crosslinked network. The introduction of these dynamic covalent bonds significantly facilitates network degradation, as their rapid cleavage under alkaline conditions. The experimental results robustly corroborate this dual functionality. Notably, after 21 days of storage at room temperature, the experimental group (EP-B-M-0.5%) exhibited a remarkably low curing conversion of only 12.2%, along with a minimal increase in viscosity of just 0.05 Pa·s@80 ℃. In sharp contrast, the control group (EP-M-0.5%) reached a conversion of 70.8% and became fully hardened within the identical storage period, underscoring the critical role of B-N coordination in extending the usable working window. Furthermore, the mechanical and thermomechanical properties of EP-B-M-0.5% remained highly stable throughout the storage period; the tensile strength and glass transition temperature (Tg) showed only marginal variations of +7.6% and +2.2%, respectively, suggesting negligible post-curing or structural alteration during storage. In accelerated degradation tests conducted in a 1 mol/L NaOH aqueous solution, the fully cured EP-B-M-0.5% network demonstrated a degradation rate 4.5 times higher than that of the control EP-M-0.5% sample, unequivocally demonstrating the efficacy of incorporating borate ester junctions in promoting rapid hydrolytic decomposition of the thermoset. Overall, this work offers a promising and operationally simple approach for advancing the processing technology of high-performance epoxy resins while aligning with the principles of green and recyclable material development.

Key words： epoxy resin; B-N coordination; one-component; storage stability; degradation

Cite this article

孙晓冉 , 刘子宇 , 刘敬楷 , 刘小青 . The Latent Curing and Highly Efficient Degrading Epoxy System based on B-N Coordination[J]. Acta Chimica Sinica, 0 : 26060207 -26060207 . DOI: 10.6023/A26060207

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