We correlate the terminal relaxation of supramolecular polymer networks, based on unentangled telechelic poly(isobutylene) linear chains forming micellar end-group clusters, with the microscopic chain dynamics as probed by proton NMR. For a series of samples with increasing molecular weight, we find a quantitative agreement between the terminal relaxation times and their activation energies provided by rheology and NMR. This finding corroborates the validity of the transient-network model and the special case of the sticky Rouse model, and dismisses more dedicated approaches treating the terminal relaxation in terms of micellar rearrangements. Also, we confirm previous results showing reduction of the activation energy of supramolecular dissociation with increasing molecular weight and explain this trend with an increasing elastic penalty, as corroborated by small angle x-ray scattering data.

中文翻译：

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形成簇的超分子聚合物网络的终端流动：单链松弛还是胶束重组？

我们关联超分子聚合物网络的终端松弛，基于形成胶束端基簇的无缠结的远螯聚（异丁烯）线性链，与质子NMR探测到的微观链动力学相关。对于一系列分子量增加的样品，我们发现了流变学和NMR在末端弛豫时间与它们的活化能之间的定量协议。这一发现证实了瞬态网络模型和粘性Rouse模型的特殊情况的有效性，并且摒弃了更专门的方法来处理胶束重排的末端弛豫。此外，我们确认了先前的结果，表明随着分子量的增加，超分子解离的活化能降低，并用弹性惩罚增加来解释这种趋势，