Department of Biomaterials Chemistry, Chair of Analytical Chemistry and Biomaterials, Faculty of Pharmacy, Medical University of Warsaw, 1 Banacha Str., 02-097 Warsaw, Poland.
Department of Environmental Health Sciences, Faculty of Pharmacy, Medical University of Warsaw, 1 Banacha Str., 02-097 Warsaw, Poland.
Molecules. 2022 Feb 8;27(3):1139. doi: 10.3390/molecules27031139.
Aliphatic polyesters are the most common type of biodegradable synthetic polymer used in many pharmaceutical applications nowadays. This report describes the ring-opening polymerization (ROP) of l-lactide (L-LA), ε-caprolactone (CL) and glycolide (Gly) in the presence of a simple, inexpensive and convenient PEG200-BiOct catalytic system. The chemical structures of the obtained copolymers were characterized by H- or C-NMR. GPC was used to estimate the average molecular weight of the resulting polyesters, whereas TGA and DSC were employed to determine the thermal properties of polymeric products. The effects of temperature, reaction time, and catalyst content on the polymerization process were investigated. Importantly, the obtained polyesters were not cyto- or genotoxic, which is significant in terms of the potential for medical applications (e.g., for drug delivery systems). As a result of transesterification, the copolymers obtained had a random distribution of comonomer units along the polymer chain. The thermal analysis indicated an amorphous nature of poly(l-lactide--ε-caprolactone) (PLACL) and a low degree of crystallinity of poly(ε-caprolactone--glycolide) (PCLGA, = 15.1%), in accordance with the microstructures with random distributions and short sequences of comonomer units ( = 1.02-2.82). Significant differences in reactivity were observed among comonomers, confirming preferential ring opening of L-LA during the copolymerization process.
脂肪族聚酯是当今许多药物应用中使用的最常见的可生物降解合成聚合物。本报告描述了在简单、廉价和方便的 PEG200-BiOct 催化体系存在下，l-丙交酯 (L-LA)、ε-己内酯 (CL) 和甘醇酸 (Gly) 的开环聚合 (ROP)。所得共聚物的化学结构通过 H-或 C-NMR 进行了表征。GPC 用于估计所得聚酯的平均分子量，而 TGA 和 DSC 用于确定聚合物产物的热性能。研究了温度、反应时间和催化剂含量对聚合过程的影响。重要的是，所得聚酯没有细胞毒性或遗传毒性，这对于医学应用（例如，用于药物传递系统）具有重要意义。由于酯交换反应，所得共聚物在聚合物链上具有单体单元的无规分布。热分析表明聚(l-丙交酯-ε-己内酯) (PLACL) 具有无定形性质，聚(ε-己内酯-甘醇酸) (PCLGA， = 15.1%) 的结晶度较低，这与具有无规分布和短序列单体单元的微观结构一致（= 1.02-2.82）。观察到单体之间的反应性存在显著差异，这证实了在共聚过程中 L-LA 的优先开环。
