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[交流] Degradable thermosets via orthogonal polymerizations of a single monomer

Degradable thermosets via orthogonal polymerizations of a single monomer

通过单一单体的正交聚合制备可降解热固性塑料

▲ 作者:Reagan J. Dreiling, Kathleen Huynh & Brett P. Fors

▲ 链接:https://www.nature.com/articles/s41586-024-08386-w

▲ 摘要:在此,我们提出了一种具有可降解热固性的一次性合成模块。它来自商业上可行的、生物来源的单体2,3-二氢呋喃(DHF)。在钌催化剂和光酸发生器的存在下,DHF进行缓慢开环复分解聚合,得到软聚合物;然后,暴露在光线下后触发强酸生成,促进同一DHF单体的阳离子聚合,从而产生空间交联,增加材料强度。通过操纵催化剂负载和光照,我们可以获得具有跨越数量级的物理性质的材料,并实现空间分辨率的材料域。

重要的是,基于DHF的热固性材料经过刺激可以逐渐降解,通过温和加热进行回收。在单一官能团上使用两种不同的聚合机制,可以合成具有精确控制性能的可降解和可回收的热固性材料。

▲ Abstract:Here we present a modular, one-pot synthesis of degradable thermosets from the commercially available, biosourced monomer 2,3-dihydrofuran (DHF). In the presence of a ruthenium catalyst and photoacid generator, DHF undergoes slow ring-opening metathesis polymerization to give a soft polymer; then, exposure to light triggers strong acid generation and promotes the cationic polymerization of the same DHF monomer to spatially crosslink and strengthen the material. By manipulating catalyst loading and light exposure, we can access materials with physical properties spanning orders of magnitude and achieve spatially resolved material domains. Importantly, the DHF-based thermosets undergo stimuli-selective degradation and can be recycled to the monomer under mild heating. The use of two distinct polymerization mechanisms on a single functional group allows the synthesis of degradable and recyclable thermoset materials with precisely controlled properties.
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