Incorporation of Thioacetate Pendants on a Polyalkenamer Enables High Extensibility

IF 5.1 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2024-10-24 DOI:10.1021/acs.macromol.4c02110

Roshni John Chethalen, Myounguk Kim, Juan Correa Ruiz, Chien-Hua Tu, Jordan Gray, Karen I. Winey, Alan J. Lesser, Alfred J. Crosby, E. Bryan Coughlin

引用次数: 0

Abstract

This study focuses on functionalizing polycyclooctene (PCOE) with thioacetate groups using thiol–ene click chemistry. The ethylene thioacetate (EVSA) copolymers produced vary in thioacetate incorporation (4–25 mol %) via a controlled semibatch addition technique with AIBN dosing. Copolymers with 4–14 mol % thioacetate are semicrystalline, while those with 20–25 mol % are amorphous. Increased functionalization correlates with decreased crystallinity and increased stretchability, with the highest functionalization (25 mol %) showing a modulus of 0.045 MPa and 2000% elongation at break. This behavior is due to the pseudoprecise functionalization of the thioacetate pendants and intrinsic cross-linking that occurs during melt processing. Broadband dielectric spectroscopy (BDS) indicates a low activation energy barrier (16 kJ/mol for the β process), suggesting potential self-healing applications.

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在聚烯酰胺上加入硫代乙酸酯基团可实现高延展性

本研究的重点是利用硫醇-烯点击化学将聚环辛烯（PCOE）与硫代乙酸酯基团官能化。通过使用 AIBN 配料的受控半批次添加技术，生产出的硫代乙酸乙烯酯 (EVSA) 共聚物的硫代乙酸乙烯酯含量（4-25 摩尔%）各不相同。硫代乙酸酯含量为 4-14 摩尔%的共聚物为半结晶，而含量为 20-25 摩尔%的共聚物为无定形。官能度的增加与结晶度的降低和拉伸性的增加有关，官能度最高的聚合物（25 摩尔%）的模量为 0.045 兆帕，断裂伸长率为 2000%。这种行为是由于硫代乙酸酯垂饰的假精确官能化和熔融加工过程中发生的内在交联。宽带介电光谱（BDS）显示，其活化能势垒较低（β 过程为 16 kJ/mol），这表明它具有潜在的自愈合应用价值。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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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.