Decoding the linear viscoelastic properties of model telechelic metallo-supramolecular polymers
Decoding the linear viscoelastic properties of model telechelic metallo-supramolecular polymers
复制标题
DOI：
10.1122/1.4997593
复制
发表时间：
2017-11
影响因子：
3.3
通讯作者：
Flanco Zhuge;Laurence G. D. Hawke;C. Fustin;J. Gohy;E. Ruymbeke
中科院分区：
文献类型：
--
作者：
Flanco Zhuge;Laurence G. D. Hawke;C. Fustin;J. Gohy;E. Ruymbeke
本文主要研究了纠缠远旋体金属超分子聚合物的线性粘弹性特性。后者是基于在不同性质的过渡金属离子存在下，在每个链端都有三吡啶配体功能化的线性和星形聚丙烯酸正丁酯。分别使用小振幅振荡剪切和改进的基于管的时间推进算法（TMA）对系统进行了实验和理论研究。实验数据表明，样品弛豫取决于解纠缠动力学和缔合动力学，这两个过程的重要性取决于金属离子的性质和温度。如果金属配体配合物的解离事件通过配体交换发生，则使用改进的TMA模型可以很好地描述数据。该模型包含两个拟合参数，即未关联贴纸的比例和确保所需的最长时间。
This work focuses on the linear viscoelastic properties of entangled telechelic bulk metallo-supramolecular polymers. The latter are based on linear and star poly(n-butyl acrylate)s functionalized with a terpyridine ligand at each chain extremity, in the presence of transition metal ion of varying nature. The systems are investigated both experimentally and theoretically using small amplitude oscillatory shear and a modified version of the tube-based time marching algorithm (TMA), respectively. The experimental data reveal that sample relaxation depends on both disentanglement and association dynamics, with the respective importance of these two processes depending on the nature of the metal ion and on the temperature. A good description of the data is achieved using the modified TMA model, provided that dissociation events of metal-ligand complexes occur via ligand exchange. The model contains two fitting parameters, i.e., the fraction of unassociated stickers and the longest time needed in order to ensu...