In Situ Photoresin Synthesis via Reactive Diluents for Vat Photopolymerization.

IF 5.4 2区化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY

Biomacromolecules Pub Date : 2025-10-09 DOI:10.1021/acs.biomac.5c01471

Tao Zhang, Vincent S D Voet, Rudy Folkersma, Katja Loos

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引用次数: 0

Abstract

As climate change intensifies, there is a pressing demand for sustainable alternatives to fossil-derived photoresins in additive manufacturing. While biobased systems have been explored, many rely on hazardous solvents, limiting their environmental benefits. Here, we report a one-pot, purification-free strategy for synthesizing renewable, high-performance photoresins using furan-based monomers derived from lignocellulosic biomass. Furfuryl methacrylate and 4,4'-bismaleimidodiphenylmethane (BSM) were integrated into methacrylate networks via Diels-Alder (DA) chemistry, with 2-hydroxyethyl methacrylate (HEMA) enabling high conversion (93%) under optimized conditions. Mechanical testing revealed that UV postcuring enhanced tensile strength, whereas excessive UV or solvent exposure caused oligomer leaching. Thermal postcuring activated retro-DA reactions, improving mechanical robustness and shape memory performance. Comparative studies showed aromatic DA derivatives offered superior programmability, while aliphatic analogs provided higher renewable carbon content with stable printability. This scalable, solvent-free strategy establishes a green chemistry framework for sustainable, high-performance photoresins, advancing additive manufacturing toward circular economy objectives.

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用活性稀释剂原位合成还原光聚合光树脂。

随着气候变化的加剧，在增材制造中迫切需要可持续的化石衍生光树脂替代品。虽然已经探索了生物基系统，但许多系统依赖于有害溶剂，限制了它们的环境效益。在这里，我们报告了一种一锅，无净化的策略，用于合成可再生的，高性能的光树脂，使用源自木质纤维素生物质的呋喃基单体。通过Diels-Alder （DA）化学将甲基丙烯酸糠酯和4,4′-双马来酰亚胺二苯基甲烷（BSM）整合到甲基丙烯酸酯网络中，2-甲基丙烯酸羟乙酯（HEMA）在优化条件下可实现高转化率（93%）。机械测试表明，UV后固化提高了拉伸强度，而过度的UV或溶剂暴露会导致低聚物浸出。热后固化激活逆da反应，提高机械稳健性和形状记忆性能。比较研究表明，芳香DA衍生物具有优越的可编程性，而脂肪族类似物具有较高的可再生碳含量和稳定的印刷性。这种可扩展的无溶剂战略为可持续的高性能光树脂建立了绿色化学框架，推动增材制造朝着循环经济目标发展。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Biomacromolecules 化学-高分子科学

CiteScore

10.60

自引率

4.80%

发文量

417

审稿时长

1.6 months

期刊介绍： Biomacromolecules is a leading forum for the dissemination of cutting-edge research at the interface of polymer science and biology. Submissions to Biomacromolecules should contain strong elements of innovation in terms of macromolecular design, synthesis and characterization, or in the application of polymer materials to biology and medicine. Topics covered by Biomacromolecules include, but are not exclusively limited to: sustainable polymers, polymers based on natural and renewable resources, degradable polymers, polymer conjugates, polymeric drugs, polymers in biocatalysis, biomacromolecular assembly, biomimetic polymers, polymer-biomineral hybrids, biomimetic-polymer processing, polymer recycling, bioactive polymer surfaces, original polymer design for biomedical applications such as immunotherapy, drug delivery, gene delivery, antimicrobial applications, diagnostic imaging and biosensing, polymers in tissue engineering and regenerative medicine, polymeric scaffolds and hydrogels for cell culture and delivery.