近日，以色列内盖夫本-古里安大学Weizmann, Yossi团队报道了光开关烯烃作为潜在的复分解单体用于控制聚合。相关论文于2025年12月8日发表在《自然-化学》杂志上。

学界对聚合物的认知已引发社会的根本性变革。然而，在开发创新技术以实现先进材料方面仍存在广阔空间。这一领域的前沿研究方向是开发可切换催化剂，旨在实现对聚合反应的时空控制。

研究组提出一种不同于传统以催化剂为核心的研究路径：利用四环烷-降冰片二烯异构化作为可切换单体进行开环复分解聚合。通过使用两种不同的钌基烯烃复分解引发剂，研究组实现了四种降冰片二烯衍生物的可控聚合。潜在的四环烷异构体与钌引发剂混合后能形成异常稳定的体系，可保持长达7周不发生变化。除传统加热方式外，该潜性单体还可通过金双锥体的光热响应被激活，从而进行适用于三维打印技术的高效聚合反应。基于单体特殊的潜藏特性，研究组最终开发出传统方法无法实现的一锅法二嵌段共聚策略与顺序固化工艺。

附：英文原文

Title: Photoswitchable olefins as latent metathesis monomers for controlled polymerization

Author: Lemcoff, Nir, Niv, Ronny, Iudanov, Keren, Gordon, Gil, Biswas, Aritra, Ben-Nun, Uri, Shelonchik, Ofir, Lemcoff, N. Gabriel, Weizmann, Yossi

Issue&Volume: 2025-12-08

Abstract: Our understanding of polymers has given rise to fundamental changes in society. Nonetheless, there is much room to further develop and improve creative techniques to enable advanced materials. At the frontiers of this endeavour is the development of switchable catalysts aimed at providing spatiotemporal control over polymerization reactions. Here we present an alternative to the conventional catalyst-centred approach by using quadricyclane–norbornadiene isomerization as a switchable monomer for ring-opening metathesis polymerization. The on-demand polymerization of four norbornadiene derivatives was achieved using two different ruthenium-based olefin metathesis initiators. The latent quadricyclane isomer generated remarkably stable formulations upon mixing with ruthenium initiators, remaining unchanged for up to 7weeks. In addition to conventional heating, the latent monomer could also be activated by the photothermal response of gold bipyramids, leading to highly efficient polymerization reactions amenable to 3D printing techniques. Finally, a one-pot diblock copolymerization strategy and sequential curing process inaccessible by traditional methodologies was developed, exploiting the exceptional latency of the monomers.

DOI: 10.1038/s41557-025-02011-7

Source: https://www.nature.com/articles/s41557-025-02011-7