Enhancing polyacrylate covalent adaptable networks through dynamic protection and deprotection strategies for highly reactive functional monomers
Date
2025
Authors
Chen, F.
Gao, F.
Guo, X.
Liao, L.
Gao, X.
Shen, L.
Ma, J.
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Journal article
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Chemical Engineering Journal, 2025; 507:1-11
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Abstract
The high reactivity of functionalized monomers frequently results in self-polymerization or side reactions during storage and transportation, creating substantial challenges in the development of polyacrylate covalent adaptable networks (CANs). In this study, a novel protection-deprotection mechanism for dynamic bonds was designed to enable the synthesis of novel polyacrylate CANs via emulsion polymerization. The amine-yne click reaction was utilized to protect the active propionate group, forming enamine-one ethyl methacrylate (DAEM). Polyacrylate latex was synthesized through emulsion polymerization in an aqueous phase containing DAEM and an acrylate monomer. Subsequent synthesis of polyacrylate CANs was achieved via transamination.
A series of latexes and films were prepared by adjusting the ratios of butyl acrylate (BA) to methyl methacrylate (MMA) and varying DAEM content. Results demonstrated that a P-B/M1:1.75-D4.5% film, synthesized from a B/M1:1.75-D4.5% latex with a BA to MMA ratio of 1:1.75 and 4.5 wt% DAEM, exhibited superior mechanical flexibility, excellent dynamic performance, and notable reprocessability. Polymer/carbon nanotube (CNT) nanocomposites were produced by mechanically blending CNTs with the B/M1:1.75-D4.5% latex. These nanocomposites exhibited satisfactory electrical conductivity while maintaining good dynamic behavior without compromising shape memory properties. This study introduces a novel approach to the application of highly reactive functional monomers and demonstrates significant potential for application in composite materials.
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Data source: Supplementary data, https://doi.org/10.1016/j.cej.2025.160425
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