可自修复、再加工、抗菌硅橡胶的制备及性能研究  

Self-healing,Reprocessable,and Antibacterial Silicone Rubber Enabled by Ionic Crosslinking Bonds

作　　者：祖兆基 曹雨扬 刘静雯 林子谦 张蓝月 向洪平 章明秋 Zhao-ji Zu;Yu-yang Cao;Jing-wen Liu;Zi-qian Lin;Lan-yue Zhang;Hong-ping Xiang;Ming-qiu Zhang(Guangdong Provincial Key Laboratory of Functional Soft Condensed Matter,School of Materials and Energy,Guangdong University of Technology,Guangzhou 510006;School of Biomedical and Pharmaceutical Sciences,Guangdong University of Technology,Guangzhou 510006;Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education,Key Laboratory of High Performance Polymer Based Composites of Guangdong Province,School of Chemistry,Sun Yat-Sen University,Guangzhou 510275)

机构地区：[1]广东工业大学材料与能源学院广东省功能软凝聚态物质重点实验室,广州510006 [2]广东工业大学生物医药学院,广州510006 [3]中山大学化学学院,广东省高性能树脂基复合材料重点实验室,聚合物复合材料及功能材料教育部重点实验室,广州510275

出　　处：《高分子学报》2025年第1期152-165,共14页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号52033011,52273104);广东省基础与应用基础研究基金(基金号2022A1515011972)资助。

摘　　要：以γ-二乙烯三胺丙基改性聚硅氧烷(PMAS)为基材、柠檬酸(CA)作为交联剂,制备了可自修复、再加工和抗菌的动态交联硅橡胶(PMAS-CA),并将其与碳纳米管(CNTs)复合而成硅橡胶复合材料,研究其力学性能、自修复等性能的调控机制.结果表明:PMAS经CA交联后可形成离子交联键,所构建的交联网络随温度升高而逐步解离,降温后离子交联键可重新形成.随CA用量的增加,硅橡胶的拉伸强度增大,断裂伸长率降低;当PMAS与CA之间的氨基与羧基的比值为1时,硅橡胶的力学能较好,拉伸强度为1.2 MPa,伸长率为150%.所制备硅橡胶发生断裂破坏后,在80℃下修复2 h后可恢复90%的力学性能.所制备的硅橡胶对大肠杆菌和金黄色葡萄球菌具有良好抗菌效果,同时还具有良好的细胞相容性.此外,PMAS-CA与CNTs复合后力学性能提高了2~3倍,所制备CNTs/PMAS-CA复合材料具有良好的自修复能力,在80℃下修复4 h,修复效率高于80%.该简便工艺所制备的自修复、可再加工、抗菌动态交联硅橡胶及其复合材料有望用于柔性传感等领域.In this study,γ-diethylenetriaminepropyl-modified polysiloxane(PMAS)and citric acid(CA)are used as the matrix and crosslinking agent to prepare silicone rubber(PMAS-CA)with self-healing,reprocessable,and antibacterial properties.Furthermore,the silicone rubber is compounded with carbon nanotubes(CNTs)to form silicone rubber composites,and their mechanical properties and self-healing capabilities are investigated.The results indicates that PMAS crosslinked with CA can form ionic crosslinking bonds,which progressively dissociate with increasing temperature and reassociate upon cooling.With increasing amounts of CA,the tensile strength of the silicone rubber is increased,while the elongation at break is decreased.The silicone rubber prepared from PMAS with an amine value of about 3 mmol/g and an amine-to-carboxyl ratio of 1 exhibits optimal comprehensive properties,with a tensile strength of 1.2 MPa and an elongation of 150%.After being damaged and subsequently repaired at 80℃for 2 h,the silicone rubber can recover 90%of its mechanical performance.The prepared silicone rubber also reveals good antibacterial effects against Escherichia coli and Staphylococcus aureus,and has good biocompatibility.Furthermore,the mechanical properties of the PMAS-CA composites are improved by 2 to 3 times after compounding with CNTs,and the CNTs/PMAS-CA composites exhibit excellent self-healing capabilities,with a repair efficiency of over 80%after 4 h at 80℃.Therefore,this dynamically crosslinked silicone rubber and composites prepared through the simple process,showing excellent self-healing,reprocessing,and antibacterial properties,have the potential applications in flexible sensors and other fields.

关 键 词：硅橡胶 自修复 离子键 抗菌性能 柔性电子器件 

分 类 号：TQ333.93[化学工程—橡胶工业]