荧光防污自修复水性聚氨酯的制备及性能

Preparation and performance properties of waterborne polyurethanes with fluorescent, antifouling and self-healing function

摘要:

以全氟丁基磺酰氟（PFSF）与乙二胺（EDA）为原料，反应制备中间产物N-氨乙基-全氟丁基磺酰胺（PFSF-E），然后将4-溴-1,8-萘二甲酸酐（BA）先后与2-氨基-1,3-丙二醇（AP）和PFSF-E反应制备荧光多功能扩链剂4-N-全氟丁基磺酰乙二胺-N-(2-羟基-1-羟甲基乙基)-1,8-萘二甲酰胺（BA-F），最后将BA-F引入聚氨酯中，制备了系列荧光防污自修复水性聚氨酯（BA-FPU）。基于FTIR、1HNMR、紫外-可见-近红外分光光度计、荧光光谱仪、DLS、TGA、DSC、XRD、接触角测量仪、XPS、拉力试验机和光学显微镜等表征和测试，考察BA-F的含量（加入量占BA-FPU乳液的质量百分数，下同）对BA-FPU乳液和胶膜的结构和性能的影响。结果表明：FTIR、1HNMR证实产物具有预期结构。BA-FPU乳液的粒径，以及BA-FPU胶膜荧光强度、热稳定性、结晶度、疏水性能和拉伸强度均随BA-F含量的增加而增强，BA-FPU胶膜断裂伸长率随BA-F含量的增加而降低。当BA-F含量为2.5%时，BA-FPU-2.5胶膜表面水接触角最高达112°，拉伸强度最大为36 MPa，断裂伸长率最低为410%。BA-FPU胶膜具备自修复特性，BA-F含量1%的BA-FPU-1胶膜表面的划痕在9 h后即可消失。

Abstract:

The intermediate N-aminoethyl-perfluorobutyl sulfonamide (PFSF-E) was firstly synthesized via the reaction of perfluorobutyl sulfonyl fluoride (PFSF) with ethylenediamine (EDA). Then, a fluorescent multifunctional chain extender 4-N-perfluorobutylsulfonylethylenediamine-N-(2-hydroxy-1-hydroxymethylethyl)-1,8-naphthalimide (BA-F) was prepared by sequential reactions of 4-bromo-1,8-naphthalic anhydride (BA) with 2-amino-1,3-propanediol (AP) and PFSF-E. Based on this, a series of fluorescent antifouling self-healing waterborne polyurethanes (BA-FPU) were synthesized. The structure and performance properties of the polymers, emulsions, and latex films were systematically investigated using FTIR, 1HNMR, ultraviolet-visible (UV-Vis) spectrophotometry, fluorescence spectroscopy, DLS, TGA, DSC, XRD, contact angle measurements, XPS, tensile testing, and optical microscopy. The results confirmed the successful synthesis of the target molecules. Key findings revealed that the particle size, fluorescence intensity, thermal stability, crystallinity, hydrophobicity, and tensile strength of BA-FPU exhibited a positive correlation with increasing BA-F content. The material demonstrated exceptional performance metrics, including a maximum water contact angle of 112°, tensile strength of 36 MPa, elongation at break of 410%, and complete self-healing of surface scratches within 9 hours.