基于超疏水原理的皮革用自清洁界面的制备及性能研究

The fluorocarbon polymer presents an excellent waterproof and oilproof performance, additionally, nanometer TiO2 films are known for their photocatalytic activity and stability. However, studies on the perparation and characterization of superhydrophobic surfaces by compositing are rarely reported. The present project focus on the superhydrophobic pricinple and atom transfer radical polymerization (ATRP) method，the self-cleaning leather coated with nanometer TiO2 and low surface energy fluorocarbon polymer were perpared. In this case, the fluorocarbon polymer were polymerized from TiO2 via a " graft-form" method. Based on surface and structural analysis, the effects of the morphology and form of nanometer TiO2, the structure and molecular weight of fluorocarbon polymer, and the grafting ratio on the hydrophobic and photocatalytic performance were investigated, and the key technology and structure characteristic of superhydrophobic self-cleaning films with excellent comprehensive performance were illuminated. Furthermore, the structure-property correlations will be established for superhydrophobic self-cleaning films. Meanwhile, the self-cleaning pricinple will be revealed. In summary, this project is of theoretical and practical significance for enriching the basic understanding of structure-property relationship for superhydrophobic self-cleaning films and for devloping of leather and others material with high self-cleaning performance by structure control during processing.

氟碳聚合物具有优异的疏水疏油性能，纳米二氧化钛（TiO2）薄膜有着良好的光催化活性和光稳定性，但是将二者复合制备疏水薄膜的报道还很少。本项目基于超疏水原理，利用原子转移自由基聚合（ATRP）方法，在TiO2纳米粒子表面接枝低表面能的氟碳聚合物刷，制备了自清洁皮革整理剂。结合各种表征手段，探究TiO2纳米粒子形态和结构、氟碳聚合物结构和分子量，以及接枝率等因素对薄膜疏水性能和光催化性能的影响，阐明综合性能优异的超疏水自清洁膜制备的关键技术和结构特点，建立超疏水薄膜结构与性能的关系，并进一步揭示该薄膜自清洁机理。本研究对于丰富超疏水薄膜结构与性能关系理论，以及开发高度自清洁性能的皮革及其他材料具有重要的指导意义。

本项目以制备自清洁皮革为目标，通过原子转移自由基聚合法（ATRP）在TiO2纳米粒子表面引发单体聚合，合成了带有氟碳基团的聚合物刷，并将改性后纳米粒子负载在皮革上。结合FT-IR、XPS、TGA、SEM、水接触角和光催化降解甲基橙溶液等测试手段系统研究了改性前后纳米TiO2粒子的结构、接枝率、氟碳聚合物的分子量等因素对皮革自清洁疏水性能的影响。结果表明，增加硅烷偶联剂的量，可显著提高最终产物的接枝率。含氟丙烯酸酯聚合物的接枝率最高可达46.3%，分子量最大为20070g/mol。氟碳单体在TiO2纳米粒子表面的ATRP聚合是可控的。TiO2表面接枝上氟碳聚合物后则表现出显著的疏水疏油特性，分散在二甲苯和水的中间层中。将接枝后的纳米TiO2粒子负载在植鞣革上，皮革表面接触角最大达到了150°，表现出超疏水特性。不同的氟碳聚合物对皮革的疏水性有一定的影响，单体中含氟量多（2-全氟癸基丙烯酸乙酯）的疏水性能更佳。负载有接枝氟碳聚合物的TiO2纳米粒子后，皮革具有优异的可见光光催化性能，能够降解甲基橙溶液。通过对聚合物刷的结构与皮革疏水和自清洁性能的构效关系研究，进一步阐明涂覆有接枝氟碳聚合物刷TiO2纳米粒子的皮革自清洁的机理，为开发具有高度自清洁性能的皮革及其他材料提供关键技术和理论指导。