Stachak Piotr, Łukaszewska Izabela, Hebda Edyta, Pielichowski Krzysztof
Department of Chemistry and Technology of Polymers, Faculty of Chemical Engineering and Technology, Cracow University of Technology, Warszawska 24, 31-155 Cracow, Poland.
Materials (Basel). 2021 Jun 23;14(13):3497. doi: 10.3390/ma14133497.
Polyurethanes (PUs) are a significant group of polymeric materials that, due to their outstanding mechanical, chemical, and physical properties, are used in a wide range of applications. Conventionally, PUs are obtained in polyaddition reactions between diisocyanates and polyols. Due to the toxicity of isocyanate raw materials and their synthesis method utilizing phosgene, new cleaner synthetic routes for polyurethanes without using isocyanates have attracted increasing attention in recent years. Among different attempts to replace the conventional process, polyaddition of cyclic carbonates (CCs) and polyfunctional amines seems to be the most promising way to obtain non-isocyanate polyurethanes (NIPUs) or, more precisely, polyhydroxyurethanes (PHUs), while primary and secondary -OH groups are being formed alongside urethane linkages. Such an approach eliminates hazardous chemical compounds from the synthesis and leads to the fabrication of polymeric materials with unique and tunable properties. The main advantages include better chemical, mechanical, and thermal resistance, and the process itself is invulnerable to moisture, which is an essential technological feature. NIPUs can be modified via copolymerization or used as matrices to fabricate polymer composites with different additives, similar to their conventional counterparts. Hence, non-isocyanate polyurethanes are a new class of environmentally friendly polymeric materials. Many papers on the matter above have been published, including both original research and extensive reviews. However, they do not provide collected information on NIPU composites fabrication and processing. Hence, this review describes the latest progress in non-isocyanate polyurethane synthesis, modification, and finally processing. While focusing primarily on the carbonate/amine route, methods of obtaining NIPU are described, and their properties are presented. Ways of incorporating various compounds into NIPU matrices are characterized by the role of PHU materials in copolymeric materials or as an additive. Finally, diverse processing methods of non-isocyanate polyurethanes are presented, including electrospinning or 3D printing.
聚氨酯（PU）是一类重要的聚合材料，因其优异的机械、化学和物理性能而被广泛应用。传统上，聚氨酯是通过二异氰酸酯和多元醇之间的加成聚合反应制得的。由于异氰酸酯原料的毒性及其使用光气的合成方法，近年来，不使用异氰酸酯的新型清洁聚氨酯合成路线受到了越来越多的关注。在取代传统工艺的不同尝试中，环状碳酸酯（CC）与多官能胺的加成聚合似乎是获得非异氰酸酯聚氨酯（NIPU），或者更准确地说是聚羟基聚氨酯（PHU）最有前景的方法，同时在形成聚氨酯键的过程中会生成伯羟基和仲羟基。这种方法消除了合成过程中的有害化合物，并导致制备出具有独特且可调性能的聚合材料。其主要优点包括更好的化学、机械和耐热性，并且该工艺本身不受水分影响，这是一项重要的技术特性。与传统的聚氨酯类似，NIPU可以通过共聚进行改性，或用作基质来制备含有不同添加剂的聚合物复合材料。因此，非异氰酸酯聚氨酯是一类新型的环保聚合材料。关于上述主题已经发表了许多论文，包括原创研究和广泛的综述。然而，它们没有提供关于NIPU复合材料制备和加工的汇总信息。因此，本综述描述了非异氰酸酯聚氨酯合成、改性以及最终加工的最新进展。在主要关注碳酸酯/胺路线的同时，描述了获得NIPU的方法，并介绍了它们的性能。将各种化合物引入NIPU基质的方法，以PHU材料在共聚物材料中或作为添加剂的作用为特征。最后，介绍了非异氰酸酯聚氨酯的各种加工方法，包括静电纺丝或三维打印。
