Forysiak Weronika, Lizak Agnieszka, Szweda Róża
Łukasiewicz Research Network -, PORT Polish Centre for Technology Development, ul. Stabłowicka 147, 54-066, Wrocław, Poland.
Faculty of Chemistry, University of Wrocław, 14 F. Joliot-Curie, 50-383, Wrocław, Poland.
Chemphyschem. 2024 Sep 2;25(17):e202400366. doi: 10.1002/cphc.202400366. Epub 2024 Aug 12.
Polyurethanes are commodity materials used for multiple applications. In recent years, a new category of polyurethane material has emerged, characterized by the lack of polymer molar mass dispersity, control of the monomer arrangement in the chain, and even full stereocontrol. Various multistep synthesis strategies have been developed to fabricate sequence-defined polyurethanes. However, synthesizing stereocontrolled polyurethanes with a controlled sequence is still a challenge. Polyurethanes with structural precision, as represented by biopolymers, i. e. proteins or nucleic acids, have opened new application directions for these groups of materials. It has been shown that polyurethanes can be used as biomimetics, information carriers, molecular tags, and materials with strictly controlled properties. Precise synthesis of macromolecules allows us to fine-tune the properties of polymers to specific needs. Therefore, it is essential to collect information on the sequence-structure relationship of polymers. In our work, we present synthetic pathways to make sequence and stereo-defined oligourethanes. We demonstrate that structural details, i. e., the monomer sequences and position of the stereocenter, have a tremendous effect on the thermal properties of model oligourethanes. We show that the introduction of chirality by constitutional isomerization can be used to program the thermal characteristics of polymers, which are key features for material applications.
聚氨酯是用于多种应用的商品材料。近年来，出现了一类新型聚氨酯材料，其特点是聚合物摩尔质量无分散性、链中单体排列可控，甚至完全立体可控。已经开发了各种多步合成策略来制备序列定义的聚氨酯。然而，合成具有可控序列的立体可控聚氨酯仍然是一个挑战。具有结构精确性的聚氨酯，如生物聚合物（即蛋白质或核酸）所代表的，为这些材料组开辟了新的应用方向。已经表明，聚氨酯可用作仿生材料、信息载体、分子标签以及具有严格可控性能的材料。大分子的精确合成使我们能够根据特定需求微调聚合物的性能。因此，收集有关聚合物序列 - 结构关系的信息至关重要。在我们的工作中，我们展示了制备序列和立体定义的低聚聚氨酯的合成途径。我们证明结构细节，即单体序列和立体中心的位置，对模型低聚聚氨酯的热性能有巨大影响。我们表明通过构造异构化引入手性可用于编程聚合物的热特性，这是材料应用的关键特征。
