Thermally Induced Cross-Linking of Polymers via C,H Insertion Cross-Linking (CHic) under Mild Conditions.
Thermally Induced Cross-Linking of Polymers via C,H Insertion Cross-Linking (CHic) under Mild Conditions.
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DOI：
10.1021/jacs.1c02133
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发表时间：
2021-06
影响因子：
15
通讯作者：
Jonas Kost;Alexander Bleiziffer;Dennis Rusitov;J. Rühe
中科院分区：
文献类型：
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作者：
Jonas Kost;Alexander Bleiziffer;Dennis Rusitov;J. Rühe
到目前为止，通过C，H插入交联(CHIC)反应形成表面附着的聚合物网络的研究主要集中在光化学活化上。这项研究描述了在相对温和的条件下形成(表面附着的)聚合物网络的热激活。一种基于重氮苯酯基的新型交联剂被引入到各种共聚物中，然后将其沉积在固体基质上。当被激活时，交联剂部分产生卡宾中间体，这导致整个薄膜快速、完全的交联，并通过CHIC同时表面附着到各种有机材料上。尽管该系统只需要较温和的条件(即低于100°C)即可激活，但在室温下可观察到较长的保质期。所提出的系统可能在从涂层到相当复杂的几何形状的广泛应用中有用。我们展示了排斥蛋白质的薄膜与(橡胶)管内表面的共价结合，并通过“烙铁”方法产生了图案化结构。为此，将热结构压在重氮聚合物涂层表面上，在接触区导致快速交联，而在所有其他区域，聚合物保持可溶，并在随后的提取过程中被洗去。
The focus of studies performed so far on the formation of surface-attached polymer networks by C,H insertion cross-linking (CHic) reaction has been largely on photochemical activation. This study describes the thermal activation of the formation of (surface-attached) polymer networks under comparably mild conditions. A novel cross-linker, based on a diazo phenyl ester group, is incorporated into various copolymers, which are subsequently deposited on solid substrates. Upon activation, the cross-linker moieties generate carbene intermediates, which lead to rapid, complete cross-linking of the whole film and simultaneous surface attachment to various organic materials via CHic. Although this system requires only comparably mild conditions (i.e., below 100 °C) to become activated, a long shelf life at room temperature is observed. The presented system might be useful in a wide range of applications, from coatings to rather complex geometries. We demonstrate the covalent binding of protein-repellent thin films to the inner surface of (rubber) tubes and the generation of patterned structures by a "branding iron" approach. For this a hot structure is pressed onto a diazo polymer coated surface, leading in the contact zone to fast cross-linking while in all other areas the polymer remains soluble and is washed off during subsequent extraction.