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用于SLA 3D打印的生物基多组分增强树脂的连续可持续生产。

Continuous Sustainable Production of Biobased Multicomponent Enhanced Resin for SLA 3D Printing.

作者信息

Jašek Vojtěch, Bartoš Otakar, Lavrinčíková Veronika, Fučík Jan, Figalla Silvestr, Kameníková Eliška, Přikryl Radek

机构信息

Institute of Materials Chemistry, Faculty of Chemistry, Brno University of Technology, Brno 61200, Czech Republic.

Institute of Environmental Chemistry, Faculty of Chemistry, Brno University of Technology, Brno 612 00, Czech Republic.

出版信息

ACS Mater Au. 2025 Mar 20;5(3):580-592. doi: 10.1021/acsmaterialsau.5c00014. eCollection 2025 May 14.

Abstract

This work focuses on biobased reactive diluents' synthesis, continuing with optimized oil-based resin precursor production. Our approach introduces vanillin methacrylate (VanMMA), cinnamyl methacrylate (CinMMA), and vanillyl dimethacrylate (VanDiMMA) synthesis using methacrylic anhydride. The introduced approach involves an innovative and available catalyst, potassium acetate, which possesses much suitable potential compared with the usually used 4-dimethylaminopyridine (DMAP). Moreover, we separated the formed secondary product, methacrylic acid (MA), and used it to modify rapeseed oil to prepare a curable thermoset. All synthesized products were structurally verified via complex cross-analysis (NMR, ESI-MS, and FTIR). The reactive systems were mixed to form a multicomponent mixture appropriate for stereolithography (SLA) and 3D printing. It was found that VanDiMMA exhibited comparable diluting properties to the commercially available and used compound, isobornyl methacrylate (IBOMA), while achieving better mechanical, thermo-mechanical, and thermal properties than IBOMA. VanDiMMA-containing SLA resin reached a tensile strength of 12.7 ± 0.3 MPa, a flexural strength of 16.8 ± 0.4 MPa, a storage modulus of 570 MPa at 30 °C, a glass-transition temperature of 83.7 °C, and the heat-resistant index of 169.5 °C.

摘要

这项工作聚焦于生物基反应性稀释剂的合成,并继续进行优化的油基树脂前驱体生产。我们的方法介绍了使用甲基丙烯酸酐合成甲基丙烯酸香兰酯(VanMMA)、甲基丙烯酸肉桂酯(CinMMA)和二甲基丙烯酸香兰酯(VanDiMMA)。所采用的方法涉及一种创新且实用的催化剂——乙酸钾,与常用的4-二甲氨基吡啶(DMAP)相比,它具有更合适的潜力。此外,我们分离出了生成的副产物甲基丙烯酸(MA),并用其改性菜籽油以制备可固化的热固性材料。所有合成产物均通过复杂的交叉分析(核磁共振、电喷雾电离质谱和傅里叶变换红外光谱)进行了结构验证。将反应体系混合以形成适合立体光刻(SLA)和3D打印的多组分混合物。结果发现,VanDiMMA表现出与市售且常用的化合物甲基丙烯酸异冰片酯(IBOMA)相当的稀释性能,同时在机械、热机械和热性能方面比IBOMA更好。含VanDiMMA的SLA树脂的拉伸强度达到12.7±0.3兆帕,弯曲强度为16.8±0.4兆帕,在30℃时的储能模量为570兆帕,玻璃化转变温度为83.7℃,耐热指数为169.5℃。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/54cf/12082353/e3442dadd945/mg5c00014_0001.jpg

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