纳米氧化锌掺杂对多孔聚氨酯薄膜表面结构和性能的影响  

Effect of Nano-ZnO Doping on Surface Microstructures and Properties of Cellular Porous Polyurethane Films

作　　者：计俞伟 薛名山[1] 李娜[2] 李坚 殷祚炷 罗一丹 JI Yu-wei;XUE Ming-shan;LI Na;LI Jian;YIN Zuo-zhu;LUO Yi-dan(School of Materials Science and Engineering,Nanchang Hangkong University,Nanchang 330063,China;School of Aeronautical Manufacturing and Engineering,Nanchang Hangkong University,Nanchang 330063,China)

机构地区：[1]南昌航空大学材料科学与工程学院,南昌330063 [2]南昌航空大学航空制造与工程学院,南昌330063

出　　处：《表面技术》2021年第7期149-157,共9页Surface Technology

基　　金：国家自然科学基金(11864024,51662032)。

摘　　要：目的通过纳米氧化锌(nano-ZnO)掺杂制备规整有序、分布均匀的蜂窝状多孔聚氨酯薄膜,并改善多孔薄膜表面的润湿性和热稳定性。方法利用nano-ZnO的极性分子特性,以溶液共混的方式将TPU用四氢呋喃(THF)溶解,添加nano-ZnO颗粒进行混合,采用微液滴模板法固化成膜,制备不同掺杂比例的nano-Zn O/TPU多孔复合薄膜。结果 nano-ZnO的质量分数为0%~50%时,薄膜表面微孔结构呈现先有序、后无序。nano-ZnO的质量分数为10%(TPU-10)时,表面微孔排列最为致密有序,表面静态接触角(CA)达到最大,为134.5°,相比于未掺杂的多孔TPU薄膜,软段熔融温度(t_(m))、硬段软化温度(t_(g))分别升高了51、8.1℃,起始热分解温度(t_(d))降低了61.1℃。nano-ZnO质量分数为40%~50%(TPU-40、TPU-50)时,经高锰酸钾(KMnO_(4))粗化及低表面能物质全氟辛基三甲氧基硅氧烷(POTS)修饰,CA达到156°以上。结论掺杂的nano-ZnO抑制了多孔薄膜制备过程中TPU体系的微相分离,使多孔复合薄膜t_(m)、t_(g)相对于TPU-0有所升高,同时由于部分软段内部的氢键被取代,导致t_(d)降低。nano-ZnO质量分数为10%时,多孔复合薄膜表面微孔排列最规则,CA达到最大值;nano-ZnO质量分数≥40%时,薄膜通过KMn O4粗化及低表面能修饰,可获得超疏水性。This paper aims to obtain a porous polyurethane(TPU)film with regular and orderly distribution of micropores,improve the micro-nano structure of the porous film surface,and improve the wettability of the film surface.The polar molecular characteristics of nano-ZnO are taken advantaged of,TPU is dissolved with tetrahydrofuran(THF)in a solution blending manner,nano-ZnO particles are added for mixing,and micro-droplet template method is used to solidify it into a film to prepare different doping ratios of Nano-ZnO/TPU porous composite film.When the content of nano-ZnO is between 0 wt%to 50 wt%,the microporous structure of the film surface is first ordered and then disordered;when the content of nano-ZnO is 10 wt%(TPU-10),the surface micropores are arranged most densely and orderly,and the static contact angle(CA)of the surface reaches the maximum of 134.5°.Compared with the undoped porous TPU film,the soft segment melting temperature(t_(m))and hard segment softening temperature(t_(g))are increased by 51℃ and 8.1℃,respectively.The decomposition temperature(t_(d))is reduced by 61.1.℃When nano-ZnO content is 40 wt%to 50 wt%(TPU-40,TPU-50),after being coarsened by potassium permanganate(KMnO_(4))and modified by POTS,the CA reaches above 156°.Doped nano-ZnO inhibited the microphase separation of TPU system during the preparation of porous thin films,and made t_(m) and t_(g) of soft segments of porous composite thin films higher than those of TPU-0,while t_(d) decreased due to the substitution of hydrogen bonds in some soft segments.When nano-ZnO content is 10 wt%,the micropores on the surface of porous composite film are arranged regularly,and CA reaches the maximum.When nano-ZnO≥40 wt%,the film can be super hydrophobic by KMnO_(4) roughening and low surface energy modification.

关 键 词：聚氨酯 纳米氧化锌 多孔薄膜 润湿性 热稳定性 超疏水 

分 类 号：TQ317.9[化学工程—高聚物工业]