Ternary formulations of bio-based grapeseed oil-based monomers for 3D printing: Effect of thiol-ene reaction on acrylic radical photopolymerization

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal Pub Date : 2025-06-08 DOI:10.1016/j.eurpolymj.2025.114068

Rafael Turra Alarcon , Alberto Cellai , Carla Cristina Schmitt , Éder Tadeu Gomes Cavalheiro , Marco Sangermano

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引用次数: 0

Abstract

The development of new renewable resin formulation for VAT 3D printing is one of the most actively researched topics in chemistry and materials science. In this sense, a good balance of sustainability and final properties should be developed. Therefore, this work aims to use grapeseed oil-GSO, acrylated seed oil-AGSO, and Trimethylolpropane tris(3-mercapto propionate) – 3SH as monomers for new printable formulations. These formulations were investigated to understand the types of reactions that can occur during photopolymerization. Therefore, two reactions can occur depending on the system: thiol-ene polymerization (TEP) and free radical polymerization (FRP). All formulations showed conversion values superior to 80% and are feasible to be applied in VAT 3D printing to print complex structures. Moreover, formulations containing a higher quantity of GSO-3SH presented biobased carbon content superior to 72% and gel content higher than 99%. Last, the amount of the TE part (GSO-3SH) affects the glass transition temperature, mechanical properties (toughness, stress, strain), and hydrophobicity. Therefore, materials with different stress, strain, and toughness can be designed using various concentrations of each monomer.

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用于3D打印的生物基葡萄籽油基单体三元配方：巯基反应对丙烯酸自由基光聚合的影响

用于增值3D打印的新型可再生树脂配方的开发是化学和材料科学中最活跃的研究课题之一。从这个意义上说，应该在可持续性和最终性能之间取得良好的平衡。因此，本研究旨在以葡萄籽油- gso、丙烯酸化籽油- agso和三甲基丙烷三（3-丙酸巯基）- 3SH为单体，制备新的可打印配方。对这些配方进行了研究，以了解在光聚合过程中可能发生的反应类型。因此，根据体系的不同，可以发生两种反应：巯基聚合（TEP）和自由基聚合（FRP）。所有配方的转换值均在80%以上，适用于增值税3D打印打印复杂结构。GSO-3SH含量较高的配方，其生物基碳含量大于72%，凝胶含量大于99%。最后，TE部分（GSO-3SH）的用量影响玻璃化转变温度、力学性能（韧性、应力、应变）和疏水性。因此，可以使用每种单体的不同浓度来设计具有不同应力、应变和韧性的材料。

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来源期刊

European Polymer Journal 化学-高分子科学

CiteScore

9.90

自引率

10.00%

发文量

691

审稿时长

23 days

期刊介绍： European Polymer Journal is dedicated to publishing work on fundamental and applied polymer chemistry and macromolecular materials. The journal covers all aspects of polymer synthesis, including polymerization mechanisms and chemical functional transformations, with a focus on novel polymers and the relationships between molecular structure and polymer properties. In addition, we welcome submissions on bio-based or renewable polymers, stimuli-responsive systems and polymer bio-hybrids. European Polymer Journal also publishes research on the biomedical application of polymers, including drug delivery and regenerative medicine. The main scope is covered but not limited to the following core research areas: Polymer synthesis and functionalization • Novel synthetic routes for polymerization, functional modification, controlled/living polymerization and precision polymers. Stimuli-responsive polymers • Including shape memory and self-healing polymers. Supramolecular polymers and self-assembly • Molecular recognition and higher order polymer structures. Renewable and sustainable polymers • Bio-based, biodegradable and anti-microbial polymers and polymeric bio-nanocomposites. Polymers at interfaces and surfaces • Chemistry and engineering of surfaces with biological relevance, including patterning, antifouling polymers and polymers for membrane applications. Biomedical applications and nanomedicine • Polymers for regenerative medicine, drug delivery molecular release and gene therapy The scope of European Polymer Journal no longer includes Polymer Physics.