Surface-Initiated Passing-Through Polymerization on a Rubber Substrate: Supplying Monomer from Swollen Substrates
Surface-Initiated Passing-Through Polymerization on a Rubber Substrate: Supplying Monomer from Swollen Substrates
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DOI：
10.1021/acs.macromol.2c00685
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发表时间：
2022-08
期刊：
影响因子：
5.5
通讯作者：
Sean T. McDermott;Shawn P. Ward;N. C. Vy;Zilu Wang;M. D. Morales-Acosta;A. Dobrynin;D. Adamson
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文献类型：
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作者：
Sean T. McDermott;Shawn P. Ward;N. C. Vy;Zilu Wang;M. D. Morales-Acosta;A. Dobrynin;D. Adamson
通过聚合是一种用于生长表面引发的聚合物刷的技术，其中单体通过扩散通过引发剂官能化的表面而供应到生长链。相对于传统的接枝自机制，这反转了单体浓度梯度，从而允许合成更厚和更密集堆积的刷。在这里，我们使用粗粒度的计算机模拟和实验技术相结合，以证明这种方法可以实现，与可溶胀的网络状基板提供单体的功能化表面，因为它们扩散出溶胀的网络。与接枝聚合物刷相比，该方法显示出更高的接触角和更大的刷质量。此外，我们观察到，通过的方法可能会导致应变诱导的结晶在刷层或刷表面，这是我们用来估计刷的厚度。该方法为大规模合成刷改性弹性基底开辟了一条道路。
Passing-through polymerization is a technique for growing surface-initiated polymer brushes where monomers are supplied to the growing chains by diffusing through the initiator-functionalized surface. This inverts the monomer concentration gradient relative to conventional grafting-from mechanisms, allowing for the synthesis of thicker and more densely packed brushes. Here we use a combination of coarse-grained computer simulations and experimental techniques to demonstrate how this approach can be implemented, with swellable network-like substrates supplying monomers to the functionalized surface as they diffuse out of the swollen network. Compared to grafting-from polymer brushes, this method shows a higher contact angle and a greater brush mass. Additionally, we observed that the passing-through approach could lead to strain-induced crystallization in the brush layer or wrinkling of the brush surface, which we used to estimate the brush thickness. The developed method opens a path for large-scale synthesis of the brush-modified elastic substrates.