Church Derek C, Peterson Gregory I, Boydston Andrew J
Department of Chemistry, University of Washington, Seattle, Washington 98195, United States.
ACS Macro Lett. 2014 Jul 15;3(7):648-651. doi: 10.1021/mz5003068. Epub 2014 Jun 17.
The effect of star versus linear polymer architecture on the rates of mechanochemically induced bond scission has been explored. We determined rate constants for chain scission of parent linear and star polymers, from which daughter fragments were cleanly resolved. These studies confirm a mechanistic interpretation of star polymer chain scission that is governed by the spanning rather than total molecular weight. We further demonstrate the preserved rate of site-selective mechanophore activation across two different polymer structures. Specifically, we observed consistent activation rate constants from three-arm star and linear polymer analogues, despite the of the star polymer being 1.5 times greater than that of the linear system.
已经探索了星形聚合物与线性聚合物结构对机械化学诱导的键断裂速率的影响。我们确定了母体线性和星形聚合物链断裂的速率常数，从中可以清晰地分辨出子片段。这些研究证实了星形聚合物链断裂的一种机理解释，即其由跨度而非总分子量决定。我们进一步证明了在两种不同聚合物结构中位点选择性机械活性基团活化速率得以保留。具体而言，我们观察到三臂星形聚合物和线性聚合物类似物的活化速率常数一致，尽管星形聚合物的[此处原文缺失部分内容]比线性体系大1.5倍。
