合成高结晶新生超高分子量聚乙烯的功能化苯氧基亚胺催化剂：低纠缠体系的等温结晶动力学

IF 3.1 2区化学 Q2 CHEMISTRY, ANALYTICAL

Thermochimica Acta Pub Date : 2025-04-05 DOI:10.1016/j.tca.2025.180000

Sheng-Li Wu , Yi Wang

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引用次数: 0

摘要

本研究比较了5F-BAOFI/MAO合成的新生低纠缠度UHMWPE （PE_30°C_60min）与分子量相似的常规高纠缠度C-UHMWPE的等温结晶动力学。Avrami动力学和Lauritzen-Hoffman分析表明，链缠结密度对结晶行为有重要影响。与C-UHMWPE相比，较少纠缠的PE_30°C_60min表现出优异的结晶性，表现出更多的结晶域和更长的结晶时间。Lauritzen-Hoffman计算量化了界面能差异：与C-UHMWPE （σe = 0.11 J·m-2）相比，PE_30°C_60min具有更低的折叠面自由能（σe = 8.16 × 10-2 J·m-2），证实了链缠结的减少促进了晶体生长动力学。这些结果表明，控制新生链纠缠的定制合成条件可以有效地调节超高分子量聚乙烯的结晶动力学和材料性能。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Functionalized phenoxy-imine catalyst for synthesizing highly crystalline nascent UHMWPEs: Isothermal crystallization kinetics of less-entangled systems

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Functionalized phenoxy-imine catalyst for synthesizing highly crystalline nascent UHMWPEs: Isothermal crystallization kinetics of less-entangled systems

This study compares the isothermal crystallization kinetics of nascent less-entangled UHMWPE (PE_30°C_60min, synthesized via 5F-BAOFI/MAO) with conventional highly entangled C-UHMWPE of similar molecular weight. Avrami kinetic and Lauritzen-Hoffman analysis revealed that chain entanglement density critically governs crystallization behavior. The less-entangled PE_30°C_60min demonstrated superior crystallizability, evidenced by more crystalline domains in longer crystallization times compared to C-UHMWPE. Lauritzen-Hoffman calculations quantified interfacial energy differences: PE_30°C_60min exhibited a lower free energy of fold surface (σ_e = 8.16 × 10^-2 J ‧ m^-2) compared to C-UHMWPE (σ_e = 0.11 J ‧ m^-2), confirming that reduced chain entanglement enhances crystal growth kinetics. These results establish that tailored synthesis conditions controlling nascent chain entanglement effectively modulate UHMWPE crystallization kinetics and material properties.

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来源期刊

Thermochimica Acta 化学-分析化学

CiteScore

6.50

自引率

8.60%

发文量

210

审稿时长

40 days

期刊介绍： Thermochimica Acta publishes original research contributions covering all aspects of thermoanalytical and calorimetric methods and their application to experimental chemistry, physics, biology and engineering. The journal aims to span the whole range from fundamental research to practical application. The journal focuses on the research that advances physical and analytical science of thermal phenomena. Therefore, the manuscripts are expected to provide important insights into the thermal phenomena studied or to propose significant improvements of analytical or computational techniques employed in thermal studies. Manuscripts that report the results of routine thermal measurements are not suitable for publication in Thermochimica Acta. The journal particularly welcomes papers from newly emerging areas as well as from the traditional strength areas: - New and improved instrumentation and methods - Thermal properties and behavior of materials - Kinetics of thermally stimulated processes