Barber Victoria J, Borden Meredith A, Alty Jill W, Tran Ly D, Koerner Hilmar, Baldwin Luke A, Alexanian Erik J, Leibfarth Frank A
Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States.
Materials and Manufacturing Directorate, Air Force Research Laboratory, Wright-Patterson AFB, Ohio 45433, United States.
Macromolecules. 2023 May 23;56(10):3679-3686. doi: 10.1021/acs.macromol.3c00125. Epub 2023 May 9.
There is a growing need for degradable polymers for applications in sustainable plastics and medical implants. To enhance the utility of degradable polymers, both better understanding of the factors that influence their degradation and new tools to modulate degradation are needed. We report the C-H xanthylation of poly(caprolactone), a biodegradable polyester, which results in changes in materials properties even at small incorporations. Despite the functionalized materials exhibiting a decrease in crystallinity and hydrophobicity, xanthylated poly(caprolactone) degrades more slowly than its unfunctionalized counterpart. To understand this rate difference, kinetic studies with a small-molecule surrogate were performed and demonstrated that functionalization adjacent to the hydrolyzable ester functional group led to slower degradation. This study illustrates how the interplay between molecular and materials characteristics can impact degradation.
在可持续塑料和医用植入物应用中，对可降解聚合物的需求日益增长。为提高可降解聚合物的实用性，既需要更好地理解影响其降解的因素，也需要新的工具来调节降解。我们报道了聚己内酯（一种可生物降解的聚酯）的C-H黄原酸化反应，即使少量引入该反应也会导致材料性能发生变化。尽管功能化材料的结晶度和疏水性有所降低，但黄原酸化聚己内酯的降解速度比未功能化的对应物更慢。为了解这种速率差异，我们用小分子替代物进行了动力学研究，结果表明与可水解酯官能团相邻的功能化会导致降解变慢。这项研究说明了分子特性与材料特性之间的相互作用如何影响降解。
