有机硅改性聚氨酯的自修复及环境响应行为  

Self-Repair and Environmental Response Behavior of Silicone Modified Polyurethane

作　　者：张晓宇 殷鹏 林文博 王若童 张禹 李宁 曾芳磊 刘海龙 伊港 王忠卫[3] Xiaoyu Zhang;Peng Yin;Wenbo Lin;Ruotong Wang;Yu Zhang;Ning Li;Fanglei Zeng;Hailong Liu;Gang Yi;Zhongwei Wang(Jiangsu Province Key Laboratory of Environmentally Friendly Polymer Materials,School of Materials Science and Engineering,Changzhou University,Changzhou 213164,Jiangsu;Shandong Dongyue Silicone Material Co.,Ltd.,Zibo 256401,China;College of Materials Science and Engineering,Shandong University of Science and Technology,Qingdao 266590,China)

机构地区：[1]江苏省环境友好高分子材料重点实验室常州大学材料科学与工程学院,江苏常州213164 [2]山东东岳有机硅材料股份有限公司,山东淄博256401 [3]山东科技大学材料科学与工程学院,山东青岛266590

出　　处：《高分子材料科学与工程》2023年第10期119-128,共10页Polymer Materials Science & Engineering

基　　金：江苏省研究生科研创新计划(KYCX22_3009);江苏省研究生实践创新计划(SJCX22_1331);山东省自然科学基金联合基金资助项目(ZR2020LFG002);山东省先进有机硅材料与技术重点,实验室开放课题(2024)。

摘　　要：通常自修复聚氨酯的耐高温性及疏水性欠佳,且存在修复手段单一、室温等温和条件下修复缓慢等问题,因此限制了自修复聚氨酯的广泛应用。文中以聚四氢呋喃二醇(PTMEG)和端羟基聚二甲基硅氧烷(PDMS-OH)与异佛尔酮二异氰酸酯(IPDI)合成预聚体,以4,4’-二氨基二苯二硫醚(ODD)作为含有动态二硫键的刚性扩链剂,4-甲基伞形酮(4-MU)作为含有可逆环结构的封端剂,制得室温下具备红外光照修复功能的有机硅改性聚氨酯(SiPU)。研究了含有二硫键的刚性扩链剂(ODD)的添加量对SiPU各项性能的影响,以及添加端羟基聚二甲基硅氧烷(PDMS-OH)对SiPU耐热性、疏水性的影响。再将自制的聚吡咯修饰碳纳米管(PPY/CNTs)作为导电填料,将其与SiPU超声共混制得具备多重响应性的自修复有机硅改性聚氨酯(CSiPU)。通过光学显微镜、3D光学干涉仪、万能试验机等证明了SiPU均可实现在室温(25℃)10μm红外光照射下的自修复,其中多元醇与扩链剂摩尔比为3:1的SiPU3修复效果最佳,全切修复效率达到88%,划痕修复效率达到100%;通过热失重分析及接触角测量表明,有机硅结构的引入使SiPU的热稳定性及疏水性有一定提升;通过数字万用表验证了CSiPU可实现对温度及化学环境的响应行为。The self-healing polyurethane usually has poor high temperature resistance and hydrophobicity,and has the problems of single repair method,isothermal at room temperature and slow repair under conditions,which limit the wide application of self-healing polyurethane.In this paper,the silicone modified polyurethane(SiPU)with infrared light repair function at room temperature was prepared by using polytetrahydrofuran glycol(PTMEG),hydroxyl terminated polydimethylsiloxane(PDMS-OH)and isophorone diisocyanate(IPDI)as prepolymer,4,4'-thiodianiline(ODD)as rigid chain extender with dynamic disulfide bond,and 4-methylumbelliferone(4-MU)as capping agent with reversible ring structure.The effects of the amount of rigid chain extender ODD containing disulfide bond on the properties of SiPU and effects of hydroxyl terminated polydimethylsiloxane(PDMS-OH)on the heat resistance and hydrophobicity of SiPU were studied.Then the self-made polypyrrole modified carbon nanotubes(PPY/CNTs)were used as conductive filler,which ultrasonically blended with SiPU to prepare a self-healing silicone modified polyurethane(CSiPU)with multiple responsiveness.It is proved by optical microscope(OM),3D optical interferometer,universal testing machine that SiPU can achieve self-healing under the condition of room temperature(25℃)10μm infrared light irradiation,and the SiPU3 with the mole ratio of polyol and chain extender of 3:1 has the best repair effect,the total cutting repair efficiency reaches 88%,and the scratch repair efficiency reaches 100%;the thermogravimetric analysis and contact angle measurement show that the introduction of silicone structure improves the thermal stability and hydrophobicity of SiPU;the response behavior of CSiPU to temperature and chemical environment is verified by digital multimeter.

关 键 词：有机硅 自修复 聚氨酯 导电高分子 环境响应 碳纳米管 

分 类 号：TQ323.8[化学工程—合成树脂塑料工业]