Kleybolte Magdalena M, Winnacker Malte
Wacker-Chair of Macromolecular Chemistry, Technical University Munich, Lichtenbergstraße 4, Garching bei München, 85748, Deutschland.
Catalysis Research Center (CRC), Technical University Munich, Ernst-Otto-Fischer-Straße 1, Garching bei München, 85748, Deutschland.
Macromol Rapid Commun. 2024 Feb;45(3):e2300524. doi: 10.1002/marc.202300524. Epub 2023 Nov 27.
Polyamides (PA) are among the most essential and versatile polymers due to their outstanding characteristics, for example, high chemical resistance and temperature stability. Furthermore, nature-derived monomers can introduce hard-to-synthesize structures into the PAs for unique polymer properties. Pinene, as one of the most abundant terpenes in nature and its presumable stability-giving bicyclic structure, is therefore highly promising. This work presents simple anionic ring-opening polymerizations of β-pinene lactam (AROP) in-bulk and in solution. PAs with high molecular weights, suitable for further processing, are produced. Their good mechanical, thermal (T s up to 440 °C), and transparent appearance render them promising high-performance biomaterials. In the following, the suitability of different initiators is discussed. Thereby, it is found that NaH is the most successful for in-bulk polymerization, with a degree of polymerization (DP) of about 322. For solution-AROP, iPrMgCl·LiCl is successfully used for the first time, achieving DPs up to about 163. The obtained PAs are also hot-pressed, and the dynamic mechanical properties are analyzed.
聚酰胺（PA）因其出色的特性，如高耐化学性和温度稳定性，而成为最重要且用途广泛的聚合物之一。此外，天然衍生的单体可以将难以合成的结构引入聚酰胺中，从而赋予聚合物独特的性能。蒎烯作为自然界中最丰富的萜烯之一，以及其可能赋予稳定性的双环结构，因此极具潜力。这项工作展示了β-蒎烯内酰胺的本体和溶液中的简单阴离子开环聚合反应（AROP）。制备出了适合进一步加工的高分子量聚酰胺。它们良好的机械性能、热性能（玻璃化转变温度高达440°C）和透明外观使其成为有前景的高性能生物材料。接下来，讨论了不同引发剂的适用性。结果发现，氢化钠对于本体聚合最为成功，聚合度（DP）约为322。对于溶液AROP，异丙基氯化镁·氯化锂首次成功使用，实现了高达约163的聚合度。所得聚酰胺还进行了热压，并分析了动态机械性能。
