通过增加侧链长度分布增强聚甲基丙烯酸烷基酯的瞬态伸长硬化

IF 5.2 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2025-04-14 DOI:10.1021/acs.macromol.5c00042

Shilong Wu, Huanhuan Yang, Quan Chen

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引用次数: 0

摘要

在这项研究中，我们研究了侧链长度分布对聚合物熔体瞬态伸长硬化行为的影响。对于纠缠或未纠缠的体系，我们成功地制备了一系列样品，聚（甲基丙烯酸丁酯），聚（甲基丙烯酸甲酯-甲基丙烯酸共己酯）和聚（甲基丙烯酸甲酯-甲基丙烯酸共十二烷基），分别缩写为PBMA， P（MMA-co-HMA）和P(MMA-co-LMA)，它们具有相同的平均侧链长度和相似的重量-平均分子量。这些样品的线性粘弹性行为相似，但非线性拉伸行为却截然不同。瞬态应变硬化随侧链长度分布的增加而增强，依次为PBMA <；P (MMA-co-HMA) & lt;P(MMA-co-LMA)，对于未纠缠或纠缠系列都是一致的。鉴于这种一致性，详细的硬化行为是不同的，其中未纠缠的样品在劳斯魏森伯格数WiR >处表现出增厚；在高WiR >处变薄；1，这可以解释为有限的拉伸非线性弹性和链条高度拉伸和排列时的摩擦减少的结合。摩擦减少的程度取决于侧链相互渗透的长度分布。相比之下，即使在WiR低于1时，纠缠样品也表现出一致的变薄，这是由于流动引起的解纠缠的同时发生。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Enhancement of Transient Elongational Hardening of Poly(alkyl methacrylate) via Increase of Side-Chain Length Distribution

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Enhancement of Transient Elongational Hardening of Poly(alkyl methacrylate) via Increase of Side-Chain Length Distribution

In this study, we investigated the effect(s) of side-chain length distribution on the transient elongational hardening behavior of polymer melts. For either entangled or unentangled systems, we successfully prepared a series of samples, poly(butyl methacrylate), poly(methyl methacrylate-co-hexyl methacrylate), and poly(methyl methacrylate-co-lauryl methacrylate), abbreviated as PBMA, P(MMA-co-HMA), and P(MMA-co-LMA), respectively, that have the same average length of side chains and similar weight-average molecular weight. These samples exhibited quite different nonlinear elongational behavior despite a similarity of their linear viscoelastic behavior. The transient strain hardening is enhanced on an increase of the side-chain length distribution, namely, in the order of PBMA < P(MMA-co-HMA) < P(MMA-co-LMA), consistently for either the unentangled or entangled series. Given this consistency, the detailed hardening behavior is different, where the unentangled samples exhibit thickening at the Rouse Weissenberg number Wi_R > 0.1 and thinning at the higher Wi_R > 1, which can be explained by a combination of the finite extensional nonlinear elasticity and the frictional reduction when chains are highly stretched and coaligned. The degree of friction reduction relies on the length distribution according to the interpenetration of side chains. In comparison, the entangled samples exhibit consistent thinning even when Wi_R is lower than one, which is attributable to the concurrence of the flow-induced disentanglement.

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来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

期刊介绍： Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.