交联型自修复水性聚氨酯的合成与性能  

Synthesis and properties of crosslinked self-healing waterborne polyurethane

作　　者：党海春 武美君 边祥成 林先鸿 梁晋帆 李杰 赵剑波 张子梁 DANG Haichun;WU Meijun;BIAN Xiangcheng;LIN Xianhong;LIANG Jinfan;LI Jie;ZHAO Jianbo;ZHANG Ziliang(Department of Materials Engineering,Taiyuan Institute of Technology,Taiyuan 030008,China)

机构地区：[1]太原工业学院材料工程系,太原030008

出　　处：《工程塑料应用》2024年第8期39-45,共7页Engineering Plastics Application

基　　金：山西省重点研发项目(202102040201005)。

摘　　要：水性聚氨酯膜容易被划伤,利用双硫键引发的动态交换反应可赋予水性聚氨酯自修复能力。但动态共价键键合强度较弱,导致水性聚氨酯的自修复和力学性能难以兼得。采用聚环氧丙烷醚三醇和含双硫键的2-羟乙基二硫化物,在水性聚氨酯分子中同时引入双硫键和支化结构,制得高强度、交联型的自修复水性聚氨酯。以异氟尔酮二异氰酸酯(IPDI)、聚四氢呋喃醚二醇、聚环氧丙烷醚三醇、2-双(羟甲基)丙酸(DMPA)以及2-羟乙基二硫化物(HEDS)等为主要原料,经预聚物法合成不同DMPA/HEDS物质的量比的IPDI型交联型自修复水性聚氨酯,研究DMPA与HEDS物质的量比对水性聚氨酯乳液稳定性、水性聚氨酯胶膜力学性能和自修复性能的影响。采用傅里叶变换红外光谱(FTIR)仪和拉曼光谱对其进行结构表征,验证了含双硫键的自修复水性聚氨酯的成功合成。双硫键和支化结构的同时引入显著提高了水性聚氨酯胶膜的拉伸强度和自修复性能,当DMPA与HEDS物质的量比为1∶1时,拉伸强度从不含双硫键聚氨酯胶膜的13.1 MPa提高到24.2 MPa,自修复后强度达19.4 MPa,自修复率达80.1%。Dynamic exchange reaction exchanged by disulfide bonds can endow waterborne polyurethane with self-healing ability.However,the weak dynamic covalent bonding strength makes it difficult to achieve both self-healing and mechanical properties of polyurethane elastomers.Polyepoxypropane ether triol and 2-hydroxyethyl disulfide containing disulfide bonds were used to introduce both disulfide bonds and branched structures into polyurethane molecules,resulting in high-strength,cross-linked selfhealing waterborne polyurethane.Waterborne polyurethane emulsion was synthesized from iso-phorone diisocyanate(IPDI),polytetrahydrofuran ether glycol,polypropylene oxide ether triol,2-bis(hydroxymethyl)propionic acid(DMPA)and 2-hydrox-yethyl disulfide(HEDS).A series of cross-linked self-healing waterborne polyurethane membranes were obtained by adjusting the mole ratio of DMPA and HEDS.Fourier transform infrared spectroscopy and Raman characterization spectra results confirm the successful introduction of disulfide bonds into waterborne polyurethane.The waterborne polyurethane emulsion shows excellent storage stability.The cross-linked self-healing waterborne polyurethane membrane shows much higher tensile strength and self-healing ability than that without disulfide bonds.When the molar ratio of DMPA and HEDS is 1∶1,the tensile strength is improved from 13.1 MPa without disulfide bond to 24.2 MPa.The cross-linked self-healing waterborne polyurethane membrane shows high self-healing tensile strength of 19.4 MPa and self-healing rate of 80.1%.

关 键 词：水性聚氨酯 双硫键 交联 自修复 胶膜 

分 类 号：TQ323.8[化学工程—合成树脂塑料工业]