揭示合成和分离的 3-/7-(prop-2-ynyl)oxepan-2-one 异构体的共聚物的逆反应性和组成特征：对精确聚合物结构预测的影响,Polymer Chemistry

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揭示合成和分离的 3-/7-(prop-2-ynyl)oxepan-2-one 异构体的共聚物的逆反应性和组成特征：对精确聚合物结构预测的影响
Polymer Chemistry ( IF 4.1 ) Pub Date : 2024-04-05 , DOI: 10.1039/d4py00071d
Robert Mundil ₁ , Lívia Kanizsová ₂ , Petr Toman ₂ , Olga Kočková ₂ , Mariusz Uchman ₁

Affiliation

合成聚合物的结构-性能关系对于其合成设计至关重要。合成设计决定了材料的最终行为以及潜在应用。然而，在单体序列水平上对合成聚合物进行结构评估仍然具有挑战性。在这里，我们报告了 3- 和 7-(prop-2-ynyl)oxepan-2-one 在共聚过程中反应性的动力学研究。这些单体主要用于合成生物医学材料而不分离异构体，这可能导致不良的成分漂移，从而影响最终的性能。尽管如此，我们还是分离了两种异构体并详细研究了它们的聚合动力学。我们的筛选（共）聚合实验揭示了 3- 和 7- 异构体在均聚和共聚过程中的逆反应性。此外，根据动力学数据，我们使用 Frey等人开发的集成理想模型计算了共聚参数。并可视化共聚物的组成概况。通过将动力学实验和量子化学方法与最先进的分析技术相结合，包括核磁共振 (NMR)、尺寸排阻色谱 (SEC)、热解-气相色谱-质谱 (Py-GC-MS)、微分分析通过扫描量热法（DSC）和基质辅助激光解吸电离飞行时间质谱（MALDI-TOF MS），我们确定了梯度共聚物结构，其中在共聚后期加入了缓慢反应的3-异构体。因此，我们的研究结果可能成为预测由这些异构体组成的（共）聚合物结构的有用工具，最终为其生物医学应用开辟更多机会。

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Unveiling the reverse reactivity and composition profile of copolymers from synthesized and separated 3-/7-(prop-2-ynyl)oxepan-2-one isomers: implications for precise polymer structure prediction

The structure–property relationship of synthetic polymers is crucial for the design of their synthesis. Synthesis design determines the final behavior and thus potential applications of the material. However, structurally assessing a synthetic polymer at the level of monomeric sequences remains challenging. Here, we report the kinetic investigation of the reactivity between 3- and 7-(prop-2-ynyl)oxepan-2-one during their copolymerization. These monomers are mainly used to synthesize biomedical materials without separating the isomers, which can lead to undesirable composition drift, thereby affecting the resulting properties. Nevertheless, we separated both isomers and studied their polymerization kinetics in detail. Our screening (co)polymerization experiments revealed the reverse reactivity of 3- and 7-isomers during their homo- and copolymerization. Moreover, based on kinetic data, we calculated copolymerization parameters using the Integrated Ideal Model developed by Frey et al. and visualized the composition profile of the copolymers. By combining kinetic experiments and quantum chemical methods with state-of-the-art analytical techniques, including nuclear magnetic resonance (NMR), size exclusion chromatography (SEC), pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS), differential scanning calorimetry (DSC) and matrix-assisted laser desorption ionization-time-of-flight mass spectrometry (MALDI-TOF MS), we identified the gradient copolymer structure, whereinto the slowly reacting 3-isomer was incorporated at the late stage of copolymerization. Therefore, our findings may become a useful tool for structural predictions of (co)polymers consisting of these isomers, ultimately opening up further opportunities for their biomedical applications.

更新日期：2024-04-06

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