高强韧可重构C―N键交联弹性体的制备与性能  

Preparation and Properties of Reconfigurable Elastomers with High Strength and High Toughness Crosslinked by C―N Bonds

作　　者：黄晶 郭宝春[2] HUANG Jing;GUO Baochun(Key Laboratory of Synthesis and Biocolloids,Ministry of Education,School of Chemistry and Materials Engineering,Jiangnan University,Wuxi 214122,Jiangsu,China;School of Materials Science and Engineering,South China University of Technology,Guangzhou 510641,China)

机构地区：[1]江南大学化学与材料工程学院,合成与生物胶体教育部重点实验室,江苏无锡214122 [2]华南理工大学材料科学与工程学院,广州510641

出　　处：《功能高分子学报》2024年第1期15-22,共8页Journal of Functional Polymers

基　　金：国家自然科学基金(52303127);中央高校基本科研计划(JUSRP122016)。

摘　　要：首先以双(甲苯磺酰氧基)丙烷(BTP)为交联剂使丁苯吡橡胶(VPR)交联,生成基于对甲苯磺酸吡啶鎓盐的C―N键交联丁苯吡橡胶(VPR-BTP),然后引入铜离子(Cu2+),制得基于C―N键和Cu2+-吡啶配位键的双重动态键交联弹性体VPR-BTP-Cu。通过红外光谱、X射线光电子能谱仪、动态热机械分析仪、透射电镜等研究了Cu2+含量对VPR-BTP-Cu的结构与性能的影响。结果表明:BTP能够有效交联VPR,VPR-BTP-Cu具有良好的重构能力;同时,Cu2+的引入大幅提高了VPR-BTP的力学性能;当Cu2+的质量分数为9%时,VPR-BRP-Cu的强度和韧性分别比VPR-BTP提高了6.6和6.3倍。此外,VPR-BTP-Cu表现出可重构形状记忆功能。Elastomers have indispensable applications in our daily life as they possess unique high elasticity.However,most neat elastomers are mechanically weak and they are thermosetting,which make their recycling and reuse very challengeable.Consequently,it is of great significance to develop reprocessable elastomers with high strength and high toughness.In recent years,the introduction and development of elastomers crosslinked by dynamic bonds,including the covalent ones and the noncovalent ones,have offered very good opportunities for achieving this goal.Herein,elastomers crosslinked with dual dynamic bonds,i.e.C―N bonds based on pyridium and copper ions(Cu2+)-pyridine coordination bonds,have been reported.These elastomers(VPR-BTP-Cu)were prepared by using bis(p-toluenesulfonyloxy)propane(BTP)to crosslink styrene-butadiene-vinylpyridine rubber(VPR),followed by introducing Cu2+through immersing.The structure and properties of VPR-BTP-Cu with varied Cu2+contents were investigated using methods such as infrared spectroscopy,X-ray photoelectron spectroscopy,dynamic thermomechanical analyzer,and transmission electron microscopy.The results demonstrate that BTP can efficiently crosslink VPR,generating C―N bonds crosslinks,and the resultant VPR-BTP are reconfigurable due to the C―N transalkylation reactions at elevated temperatures.Additionally,Cu2+-pyridine coordination bonds play roles as sacrificial bonds under loading,dissipating large amount of energy and thus improving both the stiffness and toughness of the elastomers.When the Cu2+mass fraction is 9%,the strength and toughness of VPR-BTP-Cu reach 24 MPa and 36 MJ/m3,which are 7.6 and 7.3 times of those of VPR-BTP without Cu2+,respectively.Moreover,VPR-BTP-Cu presents reconfigurable shape memory performance.This work provides a new way to fabricate reconfigurable elastomers with high performance.

关 键 词：弹性体 C―N烷基交换 牺牲键 强韧化 可重构形状记忆 

分 类 号：O63[理学—高分子化学]