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<p>Integrating dynamic covalent chemistry with bio-based precursors presents a sustainable approach for designing reprocessable and functional materials for additive manufacturing. Specifically, vitrimers based on renewable resources represent a viable method for developing soft, healable, and recyclable structures through Light-based 3D printing. This work describes the synthesis of bio-based photopolymerizable vitrimer resins based on acrylated epoxidized soybean oil, glycerol-based reactive diluent, and a series of thiol crosslinkers with varying functionalities. The availability of dynamic hydroxyl and ester groups, provided by the thiol and acrylate molecules within the crosslinked networks, enabled vitrimer behavior through thermally induced transesterification that was catalyzed with a tin-based catalyst. Dynamic mechanical analysis showed the effect of different thiol crosslinkers on the mechanical properties, glass transition behavior, and dynamic adaptability of the network. The printed thiol-acrylate network could effectively relax 63% of its initial stress in just 2.6&#xa0;min at a temperature of 180&#xa0;°C, decreasing from 16&#xa0;min at 150&#xa0;°C, as revealed from the stress relaxation data. These thiol-acrylate vitrimers demonstrate thermally induced healing properties, triple-shape memory, and chemical recyclability due to their superior dynamic properties and softness, and thus can be suited for applications in soft active devices such as soft robotics.</p> Graphical Abstract <p></p>

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Eco-friendly vitrimers from soybean-based acrylates and thiol crosslinkers for photopolymerizable 3D printing

  • 期刊论文

  • 发表日期：

    2025年9月22日

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  • Viranchika Bijalwan,
  • Sravendra Rana

摘要

Integrating dynamic covalent chemistry with bio-based precursors presents a sustainable approach for designing reprocessable and functional materials for additive manufacturing. Specifically, vitrimers based on renewable resources represent a viable method for developing soft, healable, and recyclable structures through Light-based 3D printing. This work describes the synthesis of bio-based photopolymerizable vitrimer resins based on acrylated epoxidized soybean oil, glycerol-based reactive diluent, and a series of thiol crosslinkers with varying functionalities. The availability of dynamic hydroxyl and ester groups, provided by the thiol and acrylate molecules within the crosslinked networks, enabled vitrimer behavior through thermally induced transesterification that was catalyzed with a tin-based catalyst. Dynamic mechanical analysis showed the effect of different thiol crosslinkers on the mechanical properties, glass transition behavior, and dynamic adaptability of the network. The printed thiol-acrylate network could effectively relax 63% of its initial stress in just 2.6 min at a temperature of 180 °C, decreasing from 16 min at 150 °C, as revealed from the stress relaxation data. These thiol-acrylate vitrimers demonstrate thermally induced healing properties, triple-shape memory, and chemical recyclability due to their superior dynamic properties and softness, and thus can be suited for applications in soft active devices such as soft robotics.

Graphical Abstract