An innovative alternative to the synthesis of non-isocyanate polyurethanes (NIPUs) thermoset materials was thoroughly investigated. This pathway, involving the reaction between primary carbamate functions and aldehyde functions, was studied using model reactions between ethyl carbamate and different aldehydes that lead to the highlights of the key parameters as well as the first reported proposed mechanism for this reaction. In a second time, polycarbamates synthesized from two different polyols were synthesized via transcarbamoylation before participating in a polycondensation reaction with different monoaldehydes. First a linear NIPU oligomer was synthesized using a dicarbamate derived from ethylene glycol and benzaldehyde. This product was analysed by NMR spectroscopy and MALDI-TOF mass spectrometry. This oligomer exhibited low molar masses attributed to many secondary termination reactions, mainly due to the presence of acetic anhydride used as solvent in the reaction. Cross-linked NIPU materials were then synthesized without solvent, from the reaction between a tricarbamate derived from trimethylol propane and vanillin, a biobased monoaldehyde, for the first time. The process parameters for the synthesis of these materials were optimized to obtain biobased NIPU thermosetting networks with gel fraction (GF) in dimethylsulfoxide (DMSO) up to 82%, with T_g values ranging between 39 °C and 65 °C depending on the GF value. This study brings a much needed highlight on the little-known carbamate/aldehyde reaction and demonstrates its potential for the synthesis of novel biobased NIPU thermosetting coatings using a simple monoaldehyde such as vanillin.

对合成非异氰酸酯聚氨酯 (NIPU) 热固性材料的创新替代方案进行了深入研究。该途径涉及初级氨基甲酸酯官能团和醛官能团之间的反应，使用氨基甲酸乙酯和不同醛之间的模型反应进行了研究，导致关键参数的亮点以及首次报道的该反应提出的机制。第二次，由两种不同的多元醇合成的聚氨基甲酸酯通过转氨甲酰化合成，然后参与与不同单醛的缩聚反应。首先，使用衍生自乙二醇和苯甲醛的二氨基甲酸酯合成线性 NIPU 低聚物。通过NMR光谱和MALDI-TOF质谱分析该产物。这种低聚物表现出低摩尔质量，这归因于许多二级终止反应，主要是由于在反应中用作溶剂的乙酸酐的存在。然后，首次由三羟甲基丙烷衍生的三氨基甲酸酯和香草醛（一种生物基单醛）之间的反应，在没有溶剂的情况下合成了交联的 NIPU 材料。对这些材料的合成工艺参数进行了优化，以获得生物基 NIPU 热固性网络，其在二甲亚砜 (DMSO) 中的凝胶分数 (GF) 高达 82%，T 生物基单醛，第一次。对这些材料的合成工艺参数进行了优化，以获得生物基 NIPU 热固性网络，其在二甲亚砜 (DMSO) 中的凝胶分数 (GF) 高达 82%，T 生物基单醛，第一次。对这些材料的合成工艺参数进行了优化，以获得生物基 NIPU 热固性网络，其在二甲亚砜 (DMSO) 中的凝胶分数 (GF) 高达 82%，T_g值介于 39 °C 和 65 °C 之间，具体取决于 GF 值。这项研究为鲜为人知的氨基甲酸酯/醛反应带来了急需的亮点，并展示了其使用简单的单醛（如香草醛）合成新型生物基 NIPU 热固性涂料的潜力。