基于磷酸和环氧基团反应的聚己内酯弹性体的制备与性能研究

Synthesis and Properties of Poly(epsilon-caprolactone) Elastomers based on the Cross-linked Reaction of Phosphate Ester and Epoxy Derivatives

选用不同官能度和分子量的聚己内酯(PCL)多元醇,分别对其进行磷酸化或环氧化修饰.利用磷酸羟基(P-OH)和脂环族环氧基团(E)的高效反应,同时调整E/P-OH官能团的摩尔比例,在未添加任何可能具有潜在生物毒性的助剂(如催化剂,引发剂或溶剂)的条件下,成功制备了基于磷酸酯键交联的两类PCL弹性体:PCL210P/PCL309E(简称109系列)、PCL309P/PCL309E(简称99系列).PCL磷酸化、环氧化的合成及基于磷酸酯键交联的PCL弹性体的制备可通过~1H-NMR、^(31)P-NMR、FTIR等测试进行表征.通过对该交联体系的压缩力学、体外降解、水接触角、体外细胞毒性的测试和分析,表明PCL磷酸酯交联体系具有良好的力学性能、生物相容性和生物可降解性.此外,通过改变E/P-OH官能团的摩尔比例或组分官能度可在一定范围内实现PCL磷酸酯材料的力学和降解性能的调整.

Polycaprolactone（ PCL） polyols with different functionalities and molecular weights modified with phosphorylation or epoxidation were designed and synthesised,Based on the effective reaction of hydroxyl group of acidic phosphate ester（ P-OH） and alicyclic epoxy（ E）,adjusting the molar ratios of E / P-OH functional groups,without any additives（ such as catalyst,initiator or solvent） that may have some potential risk of biological toxicity when being applied in real clinical situations,two types of cross-linked PCL phosphoester elastic materials were designed and prepared： PCL210 P / PCL 309E（ being called ＂109＂for short）,PCL309 P /PCL309E（ being called ＂99＂ for short）,The structures of polyhydric alcohol of PCL modified with phosphorylation or epoxidation and cross-linked PCL phosphoester elastomers were characterized by ^1H-NMR,^31P-NMR and FTIR. The test and analysis of compressive mechanical properties,water contact angle,the performance of degradation and cells cytotoxicity in vitro,indicated that the cross-linked PCL elastomers had good mechanical properties,biocompatibility and biodegradability. Besides this,the adjustment of mechanical properties and biodegradability of the cross-linked PCL phosphoester elastic materials can be achieved within a certain range by adjusting the E / P-OH molar ratios and functionalities of PCL monomers.