Reprocessable, Self-Healing, and Creep-Resistant Covalent Adaptable Network Made from Chain-Growth Monomers with Dynamic Covalent Thionourethane and Disulfide Cross-Links

IF 5.1 Q1 POLYMER SCIENCE ACS Macro Letters Pub Date : 2024-08-16 DOI:10.1021/acsmacrolett.4c0039110.1021/acsmacrolett.4c00391

Tong Wang, Yixuan Chen, Boran Chen, Mathew J. Suazo, Nathan S. Purwanto and John M. Torkelson*,

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Abstract

We synthesized covalent adaptable networks (CANs) made from chain-growth comonomers using nonisocyanate thiourethane chemistry. We derivatized glycidyl methacrylate with cyclic dithiocarbonate (GMA-DTC), did a free-radical polymerization of n-hexyl methacrylate with GMA-DTC to obtain a statistical copolymer with 8 mol % GMA-DTC, and cross-linked it with difunctional amine. The dynamic covalent thionourethane and disulfide bonds lead to CAN reprocessability with full recovery of the cross-link density; the temperature dependence of the rubbery plateau modulus indicates that associative character dominates the dynamic response. The CAN exhibits complete self-healing at 110 °C with tensile property recovery and excellent creep resistance at 90–100 °C. Stress relaxation at 140–170 °C reveals an activation energy of 105 ± 6 kJ/mol, equal to the activation energy (E_a) of the CAN poly(n-hexyl methacrylate) backbone α-relaxation. We hypothesize that CANs with exclusively or predominantly associative dynamics have their stress-relaxation E_a defined by the α-relaxation E_a. This hypothesis is supported by stress relaxation studies on a similar poly(n-lauryl methacrylate)-based CAN.

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由具有动态共价硫代氨基甲酸乙酯和二硫化物交联的链增长单体制成的可再加工、自愈合和抗蠕变的共价适应性网络

我们利用非异氰酸酯硫代氨基甲酸酯化学合成了由链增长共聚物制成的共价适应性网络 (CAN)。我们用环状二硫代碳酸酯（GMA-DTC）对甲基丙烯酸缩水甘油酯进行了衍生，用 GMA-DTC 对甲基丙烯酸正己酯进行了自由基聚合，得到了含有 8 mol % GMA-DTC 的统计共聚物，并用双官能胺对其进行了交联。动态共价的硫代氨基甲酸乙酯键和二硫键使 CAN 具有可再加工性，并能完全恢复交联密度；橡胶高原模量的温度依赖性表明，缔合特性在动态响应中占主导地位。CAN 在 110 °C 时表现出完全的自愈性，在 90-100 °C 时可恢复拉伸性能和优异的抗蠕变性。140-170 °C 时的应力松弛显示出 105 ± 6 kJ/mol 的活化能，与 CAN 聚（甲基丙烯酸正己酯）骨架 α 松弛的活化能 (Ea) 相等。我们假设，完全或主要具有关联动力学的 CAN 的应力松弛 Ea 是由α-松弛 Ea 确定的。对类似的聚甲基丙烯酸正十二烷基酯 CAN 进行的应力松弛研究支持了这一假设。

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来源期刊

ACS Macro Letters 化学-

CiteScore

10.40

自引率

3.40%

发文量

209

审稿时长

1 months

期刊介绍： ACS Macro Letters publishes research in all areas of contemporary soft matter science in which macromolecules play a key role, including nanotechnology, self-assembly, supramolecular chemistry, biomaterials, energy generation and storage, and renewable/sustainable materials. Submissions to ACS Macro Letters should justify clearly the rapid disclosure of the key elements of the study. The scope of the journal includes high-impact research of broad interest in all areas of polymer science and engineering, including cross-disciplinary research that interfaces with polymer science. With the launch of ACS Macro Letters, all Communications that were formerly published in Macromolecules and Biomacromolecules will be published as Letters in ACS Macro Letters.