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Hydrolytic stability of aliphatic poly(carbonate-urea-urethane)s: Influence of hydrocarbon chain length in soft segment
Polymer Degradation and Stability ( IF 6.3 ) Pub Date : 2019-01-28 , DOI: 10.1016/j.polymdegradstab.2019.01.032
Magdalena Mazurek-Budzyńska , Marc Behl , Muhammad Y. Razzaq , Ulrich Nöchel , Gabriel Rokicki , Andreas Lendlein

Poly(carbonate-urethane)s (PCUs) exhibit improved resistance to hydrolytic degradation and in vivo stress cracking compared to poly(ester-urethane)s and their degradation leads to lower inflammation of the surrounding tissues. Therefore, PCUs are promising implant materials and are considered for devices such as artificial heart or spine implants. In this work, the hydrolytic stability of different poly(carbonate-urethane–urea)s (PCUUs) was studied under variation of the length of hydrocarbon chain (6, 9, 10, and 12 methylene units) between the carbonate linkages in the precursors. PCUUs were synthesized from isophorone diisocyanate and oligo(alkylene carbonate) diols using the moisture-cure method. The changes of sample weight, thermal and mechanical properties, morphology, as well as the degradation products after immersion in a buffer solution (PBS, pH = 7.4) for up to 10 weeks at 37 °C were monitored and analyzed. In addition, mechanical properties after 20 weeks (in PBS, 37 °C) were investigated. The gel content was determined based on swelling experiments in chloroform.

Based on the DSC analysis, slight increases of melting transitions of PCUUs were observed, which were attributed to structure reorganization related to annealing at 37 °C rather than to the degradation of the PCUU. Tensile strength after 20 weeks of all investigated samples remained in the range of 29–39 MPa, whereas the elongation at break εm decreased only slightly and remained in the range between 670 and 800%. Based on the characterization of degradation products after up to 10 weeks of immersion it was assessed that oligomers are mainly consisting of hard segments containing urea linkages, which could be assigned to hindered-urea dissociation mechanism. The investigations confirmed good resistance of PCUUs to hydrolysis. Only minor changes in the crystallinity, as well as thermal and mechanical properties were observed and depended on hydrocarbon chain length in soft segment of PCUUs.



中文翻译:

脂族聚(碳酸酯-脲-氨基甲酸酯)的水解稳定性:软链段中烃链长度的影响

聚(碳酸酯-氨基甲酸酯)(PCU)表现出提高的抗水解降解性和体内应力的能力与聚(酯-氨基甲酸酯)相比,其开裂及其降解导致周围组织的炎症降低。因此,PCU是有前途的植入物材料,并被考虑用于人造心脏或脊柱植入物等设备。在这项工作中,研究了在前体中碳酸酯键之间的烃链长度(6、9、10和12个亚甲基单元)变化的情况下,不同聚(碳酸酯-氨基甲酸酯-脲)(PCUU)的水解稳定性。 。使用湿固化法由异佛尔酮二异氰酸酯和低聚(碳酸亚烷基酯)二醇合成PCUU。监测并分析了样品重量,热和机械性能,形态以及降解产物在37°C下浸入缓冲溶液(PBS,pH = 7.4)中长达10周后的变化。此外,研究了20周后(在PBS中,37°C)的机械性能。基于在氯仿中的溶胀实验确定凝胶含量。

根据DSC分析,观察到PCUU的熔融转变略有增加,这归因于与37°C退火相关的结构重组,而不是PCUU的降解。20周所有研究的样品的后拉伸断裂强度保留在29-39兆帕的范围内,而伸长率ε仅略有下降,并保持在670%和800%之间的范围内。根据浸泡后长达10周的降解产物的特征,评估低聚物主要由含有脲键的硬链段组成,这可以归因于受阻尿素的解离机理。研究证实PCUU具有良好的抗水解性。仅观察到结晶度以及热和机械性能的微小变化,并且取决于PCUUs软段中的烃链长度。

更新日期:2019-01-28
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