Fully Bio-Based Polyhydroxyurethanes with a Dynamic Network from a Terpene Derivative and Cyclic Carbonate Functional Soybean Oil

Abstract

Polyhydroxyurethanes (PHUs), polyurethanes with excellent properties, are cured without poisonous isocyanate. The carbamate groups in the structure can undergo bond exchange in the presence of amino groups to improve their reprocessing and recyclability. As the demand for more "sustainable" polymers increases, research has focused on replacing fossil materials with renewable alternatives. 1,8-Menthane diamine (MDA) derived from turpentine is a potential raw material for curing with cyclic-carbonated soybean oil (CSBO) for preparing fully bio-based PHUs without solvents and catalysts. The amino groups from MDA facilitate bond exchange under autocatalysis in PHUs, and the rigid structure improves the thermal and mechanical properties of PHUs. PHUs with different cyclic carbonate/amino ratios are characterized to explain the importance of MDA in the performance of PHUs. Dynamic covalent bond exchange was studied through stress relaxation, which results in self-healing, recyclability, reprocessing, and shape memory. The mechanical properties and thermal stability can be almost completely recovered (>85%) after reprocessing several times, indicating that the network will be repaired by bond exchange. This work provides a promising strategy to utilize sustainable feedstocks for designing fully bio-based non-isocyanate polyurethanes and reveals the effect of the structure on the material properties.

Reprocessable, Self-Adhesive, and Recyclable Carbon Fiber-Reinforced Composites Using a Catalyst-Free Self-Healing Bio-Based Vitrimer Matrix

“…First, the cross-link density of the TOTGE–MDA vitrimers increases rapidly with the ratio, leading to a more stable 3D vitrimer network. Second, as previously reported in the literature, a concentration increase of rigid MDA can also improve the thermal stability.…”

Sustainable design of vanillin-based vitrimers using vinylogous urethane chemistry

“…Vitrimers, introduced by the pioneering work of Leibler et al, 9 are thermally triggered associative CANs that experience an Arrhenius-like viscosity decrease, rather than a sudden viscosity decrease, as seen for dissociative CANs upon a thermal trigger. 10 Among bio-based CANs, many types of renewable building blocks, ranging from terpenes to oils, 11,12 fatty acids, 13 fructose, 14 lipoic acid, 15 ferulic acid, 16 or vanillin, [17][18][19][20] have been incorporated into dynamic materials. Very recently, the field of bio-based CANmaterials has been reviewed.…”

Development of renewable thermosetting polymers based on grape seed oil derivatives

“…Analysis of the gel content (GC) was performed as described in the literature with a few modifications, 56 in which m 0 and m 1 were the sample mass before the experiment and after the drying process, respectively. …”