ICGM, Univ Montpellier, CNRS, ENSCM, 34 000 Montpellier, France.
IBMM, Univ Montpellier, CNRS, ENSCM, 34 000 Montpellier, France.
ACS Macro Lett. 2021 Dec 21;10(12):1454-1459. doi: 10.1021/acsmacrolett.1c00617. Epub 2021 Nov 8.
There is a growing interest surrounding morpholine-2,5-dione-based materials due to their impressive biocompatibility as well as their capacity to break down by hydrolytic and enzymatic pathways. In this study, the ring-opening (co)polymerization of leucine-derived 3S-(isobutyl)morpholine-2,5-dione (MD) and lactide (LA) was performed via ball-milling using a catalytic system composed of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 3-[3,5-bis(trifluoromethyl)phenyl]-1-cyclohexylthiourea (TU). Once the homopolymerizations of MD and LA optimized and numerous parameters were studied, the mechanochemical ring-opening copolymerization of these monomers was explored. The feasibility of ring-opening copolymerizations in mechanochemical systems was demonstrated and a range of P(MD--LA) copolymers were produced with varying proportions of MD (23%, 48%, and 69%). Furthermore, the beneficial cocatalytic effects of TU with regards to ROP control were found to be operative within mechanochemical systems. Further parallels were observed between solution- and mechanochemical-based ROPs.
由于其作为生物相容性材料的优异性能，以及通过水解和酶解途径进行分解的能力，基于吗啉-2,5-二酮的材料越来越受到关注。在这项研究中，使用由 1,8-二氮杂双环[5.4.0]十一碳-7-烯（DBU）和 3-[3,5-双（三氟甲基）苯基]-1-环己基硫脲（TU）组成的催化体系，通过球磨对亮氨酸衍生的 3S-（异丁基）吗啉-2,5-二酮（MD）和丙交酯（LA）进行开环（共）聚合。一旦对 MD 和 LA 的均聚物聚合进行了优化并研究了许多参数，就探索了这些单体的机械化学开环共聚。证明了机械化学体系中开环共聚的可行性，并制备了一系列具有不同 MD 比例（23%、48%和 69%）的 P（MD-LA）共聚物。此外，发现 TU 对 ROP 控制的有益共催化作用在机械化学体系中是有效的。在溶液和机械化学 ROP 之间也观察到了进一步的相似之处。
