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

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 <i>n</i>-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 (<i>E</i>_a) of the CAN poly(<i>n</i>-hexyl methacrylate) backbone α-relaxation. We hypothesize that CANs with exclusively or predominantly associative dynamics have their stress-relaxation <i>E</i>_a defined by the α-relaxation <i>E</i>_a. This hypothesis is supported by stress relaxation studies on a similar poly(<i>n</i>-lauryl methacrylate)-based CAN.