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Reprocessable, Self-Healing, and Creep-Resistant Covalent Adaptable Network Made from Chain-Growth Monomers with Dynamic Covalent Thionourethane and Disulfide Cross-Links
ACS Macro Letters ( IF 5.1 ) Pub Date : 2024-08-16 , DOI: 10.1021/acsmacrolett.4c00391 Tong Wang 1 , Yixuan Chen 1 , Boran Chen 1 , Mathew J Suazo 2 , Nathan S Purwanto 2 , John M Torkelson 1, 2
ACS Macro Letters ( IF 5.1 ) Pub Date : 2024-08-16 , DOI: 10.1021/acsmacrolett.4c00391 Tong Wang 1 , Yixuan Chen 1 , Boran Chen 1 , Mathew J Suazo 2 , Nathan S Purwanto 2 , John M Torkelson 1, 2
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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 (Ea) of the CAN poly(n-hexyl methacrylate) backbone α-relaxation. We hypothesize that CANs with exclusively or predominantly associative dynamics have their stress-relaxation Ea defined by the α-relaxation Ea. This hypothesis is supported by stress relaxation studies on a similar poly(n-lauryl methacrylate)-based CAN.
中文翻译：
由具有动态共价氨基甲硫基和二硫键交联的链增长单体制成的可再加工、自修复和抗蠕变共价适应性网络
我们使用非异氰酸酯硫氨酯化学合成了由链增长共聚单体制成的共价适应性网络（CAN）。我们用环状二硫代碳酸酯（GMA-DTC）衍生化甲基丙烯酸缩水甘油酯，将甲基丙烯酸正己酯与GMA-DTC进行自由基聚合，得到8 mol% GMA-DTC的统计共聚物，并用双官能胺交联。动态共价硫脲和二硫键可实现 CAN 可再加工性，并完全恢复交联密度；橡胶平台模量的温度依赖性表明关联特征主导动态响应。 CAN 在 110 °C 时表现出完全的自修复性，在 90–100 °C 时具有拉伸性能恢复和优异的抗蠕变性。 140–170 °C 下的应力松弛显示活化能为 105 ± 6 kJ/mol，等于 CAN 聚（甲基丙烯酸正己酯）主链 α-松弛的活化能 ( E a )。我们假设具有完全或主要关联动力学的 CAN 的应力松弛E a由 α 松弛E a定义。这一假设得到了对类似聚（甲基丙烯酸正月桂酯）基 CAN 的应力松弛研究的支持。
更新日期：2024-08-16
中文翻译：
由具有动态共价氨基甲硫基和二硫键交联的链增长单体制成的可再加工、自修复和抗蠕变共价适应性网络
我们使用非异氰酸酯硫氨酯化学合成了由链增长共聚单体制成的共价适应性网络（CAN）。我们用环状二硫代碳酸酯（GMA-DTC）衍生化甲基丙烯酸缩水甘油酯，将甲基丙烯酸正己酯与GMA-DTC进行自由基聚合，得到8 mol% GMA-DTC的统计共聚物，并用双官能胺交联。动态共价硫脲和二硫键可实现 CAN 可再加工性，并完全恢复交联密度；橡胶平台模量的温度依赖性表明关联特征主导动态响应。 CAN 在 110 °C 时表现出完全的自修复性，在 90–100 °C 时具有拉伸性能恢复和优异的抗蠕变性。 140–170 °C 下的应力松弛显示活化能为 105 ± 6 kJ/mol，等于 CAN 聚（甲基丙烯酸正己酯）主链 α-松弛的活化能 ( E a )。我们假设具有完全或主要关联动力学的 CAN 的应力松弛E a由 α 松弛E a定义。这一假设得到了对类似聚（甲基丙烯酸正月桂酯）基 CAN 的应力松弛研究的支持。
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