Vitrimers are covalently cross-linked polymeric materials that can be processed upon heating wherein triggerable polymer networks shuffle chemical bonds through exchange reactions without losing their network integrity. In this work, we apply vitrimers to develop recyclable thermosets derived from materials with relatively high bio-source content. We explore the reaction between ß-ketoesters derived from commercially available (2-acetoacetoxy) ethyl methacrylate (AAEMA) incorporated within isobornyl methacrylate (IBOMA, from pine sap), and a bi-functional amine (Priamine, derived from vegetable oils) to synthesize catalyst-free vitrimers. Controlled radical miniemulsion polymerization was also used to synthesize the water-borne copolymer analogs. Vitrimer nanocomposites were obtained by the incorporation of amine‐functionalized polyhedral oligomeric silsesquioxane (POSS-NH₂) at different loadings (0, 5, 10 and 20 wt%). Incorporation of 20 wt% POSS-NH₂ improved tensile modulus (from 96 to 176 MPa), tensile strength (from 2.5 to 5 MPa) and decomposition temperature (225 to 255 °C), and slowed down the relaxation rate and increased apparent activation energy of stress relaxation compared to the neat vitrimer. We further show that the vitrimers studied here and the nanocomposites containing vinylogous urethane cross-linking networks can be un-cross-linked by dissolving in excess mono-functional amine at 65 °C or recycled by grinding and remolding at 125 °C without compromising the mechanical properties.

Vitrimers是共价交联的聚合物材料，可以在加热后进行处理，其中可触发的聚合物网络通过交换反应改组化学键，而不会失去其网络完整性。在这项工作中，我们将使用vitrimers来开发可回收的热固性塑料，这些材料来自具有相对较高的生物来源含量的材料。我们探索了由掺入甲基丙烯酸异冰片酯（IBOMA，来自松树汁）中的可商购（2-乙酰乙酰氧基）甲基丙烯酸乙酯（AAEMA）衍生的β-酮酸酯与双功能胺（源自植物油的伯胺）之间的反应无催化剂的修磨剂。受控自由基微乳液聚合也用于合成水性共聚物类似物。₂）以不同的负载量（0、5、10和20wt％）。掺入20 wt％的POSS-NH _2可改善拉伸模量（从96到176 MPa），拉伸强度（从2.5到5 MPa）和分解温度（225到255°C），并减慢弛豫速率并增加表观活化与纯净微晶纤维素相比，应力松弛的能量更大。我们进一步表明，本文研究的三聚体和含有乙烯基类氨基甲酸酯交联网络的纳米复合材料可通过在65°C的条件下溶解于过量的单官能胺中进行未交联，​​或通过在125°C的条件下进行研磨和重塑而再循环，而不会损害机械性能。