Kamran Muhammad, Kay Andrew, Davidson Matthew G
Institute for Sustainability, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
ACS Sustain Chem Eng. 2024 Aug 29;12(37):13798-13809. doi: 10.1021/acssuschemeng.4c03498. eCollection 2024 Sep 16.
Efficient and sustainable transformation of biomass-derived chemicals to materials with the potential to replace conventional fossil-derived polymers is considered a major challenge. In this work, we disclose the synthesis of a novel furan-based α,ω-diene monomer following a facile, green, and energy-efficient process from fully renewable starting materials. The multifunctional monomer was produced by the base-catalyzed cross-aldol condensation of 10-undecenal (UA) and 2,5-diformylfuran (DFF) under mild conditions, providing the desired product in good yields. By employing the new monomer, fully biobased polymers were prepared in good molecular weights ( up to 31 kg/mol) by acyclic diene metathesis (ADMET) polymerization using Grubb's second-generation catalysts. The structure-property investigation of the polymers revealed in the range of -16 to 5 °C, high thermal stability, good hydrophobicity, and photoactive properties. Owning to the presence of amenable functional groups, the resultant polymer was also subjected to postpolymerization modifications. The effect of these modifications on the polymer properties showed enhanced crystallization attributed to hydrogen bonding interactions. This work demonstrates a scalable and environmentally benign approach to access structurally novel and versatile materials exhibiting interesting properties from 100% biobased resources.
将生物质衍生的化学品高效且可持续地转化为有可能替代传统化石衍生聚合物的材料被认为是一项重大挑战。在这项工作中，我们公开了一种新型呋喃基α,ω-二烯单体的合成方法，该方法采用简便、绿色且节能的工艺，原料完全可再生。这种多功能单体是通过在温和条件下，10-十一烯醛（UA）和2,5-二甲酰基呋喃（DFF）的碱催化交叉羟醛缩合反应制备而成，产率良好。通过使用这种新型单体，采用格拉布第二代催化剂，通过开环易位聚合（ADMET）制备出了分子量良好（高达31 kg/mol）的全生物基聚合物。对这些聚合物的结构-性能研究表明，其玻璃化转变温度在-16至5℃范围内，具有高热稳定性、良好的疏水性和光活性。由于存在适宜的官能团，所得聚合物还进行了后聚合改性。这些改性对聚合物性能的影响表明，由于氢键相互作用，结晶度有所提高。这项工作展示了一种可扩展且环境友好的方法，能够从100%生物基资源中获得具有有趣性能的结构新颖且用途广泛的材料。
