聚丙烯酸酯/纳米ZnO复合皮革涂饰剂微结构与性能调控

To solve the blindness of performance regulation and control during the research of polyacrylate/nano-ZnO composite leather finishing agent, a serials of polyacrylate/nano-ZnO composite for leather finishing are prepared with different structures of ZnO nanoparticles based on the previours research. The structure change rules of ZnO nanoparticles and polyacrylate latex particles, distribution of ZnO nanoparticles during the preparation, film-forming and finishing processes of polyacrylate/nano-ZnO composite leather finishing agents are studied systematically. The relationship between the structure of ZnO nanoparticles and the properties of polyacylate/nano-ZnO composite leather finishing agents are built by analyzing and summarizing the influence of the structure of ZnO nanoparticles on properties of films and leather finished by polyacrylate/nano-ZnO composite. In which, the structure change of ZnO nanoparticles and polyacrylate latex particles during finishig processes of polyacrylate/nano-ZnO composite leather finishing agents and the relationship between the structure of ZnO nanoparticles and the properties of polyacrylate/nano-ZnO composite leather finishing agents have not been reported. These work will offer theoretical foundation to designing and regulating properties of high quality polyacrylate/nano-ZnO composite leather finishing agent.

针对聚丙烯酸酯/纳米ZnO复合皮革涂饰剂研究过程中性能调控的盲目性，在前期研究基础上，提出采用不同结构的纳米ZnO制备系列聚丙烯酸酯/纳米ZnO复合皮革涂饰剂，系统研究制备过程中、成膜过程中及涂饰过程中纳米ZnO结构的变化、纳米ZnO的分布状态、聚丙烯酸酯乳胶粒结构的变化，通过归纳分析纳米ZnO结构与聚丙烯酸酯/纳米ZnO复合皮革涂饰剂所成薄膜及涂饰后革样各项性能间相互影响的规律，建立纳米ZnO结构与复合皮革涂饰剂性能间的相关性。其中所涉及的涂饰过程中纳米ZnO结构及聚丙烯酸酯乳胶粒结构的变化和纳米ZnO结构与复合皮革涂饰剂性能相关性的研究尚未见文献报道。期望通过本研究为高性能聚丙烯酸酯/纳米ZnO复合皮革涂饰剂的设计与性能调控提供理论依据。

本项目通过改变制备方法及调节工艺条件成功制备了不同形貌实心纳米ZnO、不同形貌中空纳米ZnO及不同尺寸球形纳米ZnO，并提出了相应的生长机理。将所制备的不同形貌实心纳米ZnO、不同形貌中空纳米ZnO、不同尺寸球形纳米ZnO引入到聚丙烯酸酯乳液中对复合乳液的形貌及稳定性进行研究，同时研究不同制备方法对复合乳液形貌及稳定性的影响，发现实心纳米ZnO和中空纳米ZnO的形貌、尺寸及用量对复合乳液外观以及稳定性没有显著影响。通过物理共混法制备的聚丙烯酸酯/ZnO纳米棒复合乳液ZnO纳米棒包覆在乳胶粒周围，而采用原位聚合法可使ZnO纳米棒全部进入乳胶粒内部。复合乳液成膜后，引入花状ZnO的复合薄膜抗菌性能较好、透水汽性、耐水性最优；引入球形ZnO的复合薄膜抗菌性能、机械性能较好。中空ZnO在聚丙烯酸酯薄膜中分散均匀，且基本保持了中空ZnO的原有形貌，但引入球状中空ZnO的复合薄膜性能最优，引入海胆状中空ZnO的复合薄膜次之，引入柱状中空ZnO的复合薄膜最差。复合薄膜的抗菌性能均随纳米ZnO尺寸的增大而降低。将含有不同形貌实心和中空纳米ZnO的复合乳液应用于皮革涂饰中，发现采用聚丙烯酸酯/球形ZnO纳米复合乳液、聚丙烯酸酯/花状ZnO纳米复合乳液涂饰后革样的抗菌效果较好，其对白色念珠菌的抑菌率分别为77.78%和75.0%，对霉菌的抑菌率分别为93.33%和96.33%。聚丙烯酸酯/球状中空ZnO复合乳液涂饰后革样的耐水性、透水汽性、透气性及力学性能最优。