Correlation Between Segmental Order Parameter and Entanglement Length in a Monodisperse Comb Polymer

This Dataset comprises the raw data contained in the figures of our journal article in Macromolecules 2024 (DOI: 10.1021/acs.macromol.4c02015) and its Supporting Information (SI). We provide a preprint of the initially submitted article including the SI for reference to the figures and their captions, necessary to use the data. Note that Fig. S1 was added upon revision, so Fig. S2 of the published SI is Fig. S1 of the SI that is part of the preprint. Please also check the published article in Macromolecules. For copyright details and licensing we refer to the published article and the publisher. Here is the abstract of the article:

The motion of a polymer chain within a hypothetical confining tube leads to arise a segmental order parameter. This parameter is assessed via multiple-quantum (MQ) NMR experiments. In both polymer networks and entangled melts, the order parameter is proportional to the inverse of the number of segments between two covalent crosslinks or physical entanglements. In entangled polymer networks, the entanglements have usually been considered as additional but temporary crosslinks and the contribution of the physical and chemical constraints are assumed additive. However, it was revealed by computer simulation results that this assumption is not valid for lowly crosslinked polymer networks; instead, the segmental order parameter was shown to scale with 1/√(N_e N_c ), N_c and N_e being the number of segments between crosslinks and entanglements, respectively [M. Lang and J.-U. Sommer, Phys. Rev. Lett. 2010, 104, 177801]. An experimental confirmation remains elusive due to challenges in distinguishing the contributions of entanglements and crosslinks, as well as the long averaging timescales involved. In this study, we assess this correlation by examining chain dynamics in a monodisperse polyisoprene comb, utilized as a model system. To model chain dynamics in this system, the dynamic dilution model, originally designed for predicting the rheological behavior of star and branched polymers, has been modified to facilitate its application in the analysis of MQ NMR signals. We also address some of its shortcomings.

本数据集包含发表于《Macromolecules》2024年期刊文章（DOI: 10.1021/acs.macromol.4c02015）及其补充材料（Supporting Information, SI）中所有附图的原始数据。我们提供了初始投稿版本的完整文章及补充材料，以供使用者参考附图及其图注——这是正确使用本数据集的必要前提。需注意：修订阶段新增了图S1，因此正式发表版补充材料中的图S2，对应预印本补充材料中的图S1。请同时参阅正式发表于《Macromolecules》的期刊文章。版权及授权相关事宜，请参见正式发表文章及出版方说明。

以下为本研究文章的摘要：

受限管模型下的聚合物链运动可产生分段序参数（segmental order parameter），该参数可通过多量子（Multiple-Quantum, MQ）核磁共振（Nuclear Magnetic Resonance, NMR）实验进行表征。在聚合物网络与缠结熔体中，该序参数与两个共价交联点或物理缠结点之间的链段数成反比。传统研究认为，在缠结聚合物网络中，缠结可视为额外的临时性交联点，物理约束与化学约束的贡献具有可加性。然而，计算机模拟结果表明，该假设对于低交联度聚合物网络并不成立：过往研究显示，分段序参数的尺度关系为1/√(N_e N_c)，其中N_c与N_e分别为交联点间与缠结点间的链段数[M. Lang与J.-U. Sommer, 《物理评论快报（Physical Review Letters）》2010, 104, 177801]。由于难以区分缠结与交联的实验贡献，且该类实验所需的平均时间尺度极长，该相关性始终缺乏直接的实验验证。本研究以单分散聚异戊二烯梳型聚合物为模型体系，通过研究其链动力学行为验证了该相关性。为适配本研究的分析需求，我们对原本用于预测星型与支化聚合物流变行为的动态稀释模型（dynamic dilution model）进行了修改，以适配多量子核磁共振信号的分析，并修正了该模型的部分固有缺陷。