纳米SiO_2表面引发接枝含短全氟碳侧链嵌段共聚物P(MMA-b-C_6SA)的合成及其性能研究  

Fluorinated Hybrid Material Synthesized by Surface Initiated ARGET ATPR with Excellent Self-cleaning Property

作　　者：钱涛[1,2] 汪涓涓[3] 张庆华[1] 詹晓力[1] 陈丰秋[1] 

机构地区：[1]浙江大学化学工程与生物工程学院,杭州310027 [2]杭州吉华高分子材料股份有限公司,杭州311228 [3]杭州娃哈哈集团有限公司,杭州310018

出　　处：《高分子学报》2016年第7期910-918,共9页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号21276224;21476195;21576236);浙江省自然基金(基金号LY14B060008)资助项目

摘　　要：通过ARGET ATRP(电子转移催化剂再生原子转移自由基聚合)法,以甲基丙烯酸甲酯(MMA)、丙烯酸[N-甲基全氟己烷磺酰胺基]乙酯(C_6SA)为单体,利用干式化学接枝法合成的SiO_2-NH-Br为引发剂,分步接枝得到了表面性能优异的有机/无机复合微-纳结构材料SiO_2-P(MMA-b-C_6SA).该材料经氢氟酸刻蚀后,采用凝胶渗透色谱(GPC)测定了接枝聚合物的分子量及其分布,结果表明在纳米SiO_2表面生长出了分子结构可控的嵌段聚合物.透射电镜观察SiO_2-P(MMA-b-C_6SA)复合物形貌呈现均匀分散的球形颗粒,表明所制备的有机/无机复合物在有机溶剂中具有良好的分散性.热重分析结果表明,该材料化学结构均一,并具有良好的热稳定性.本文采用具有工业应用前景的ARGET ATRP法,将环境友好的含氟单体(C_6SA)接枝在无机粒子表面,赋予其低表面能特性,使其水接触角达到143°,HD的静态接触角达到90°,表现出了优异的疏水疏油性能,并具有自清洁的性能.A novel hybrid material synthesized by grafting fluorinated block polymer chains to silica nanoparticles via surface-initiated activators generated by electron transfer atom transfer radical polymerization （SI-ARGET ATRP） was proposed. The components of the block copolymer 2-[ [ [ [ 2-（perfluorohexyl） ]- sulfonyl] methyl ]-amino] ethyl-acrylate （CsSA） and methyl methacrylate were well designed, and verified by gel permeation chromatography measurements. Monodispersed silica nanoparticles prepared by Stober method and grafted by the fluorinated block eopolymer could disperse well in the organic solvent. The form of fluorinated block copolymer grafted silica nanoparticles was confirmed by TEM. The composition and chemical structure were studied by FTIR and 1H-NMR. The presence of hierarchical multi-scale surface roughness in the samples was observed by scanning electron microscopy （SEM） and atomic force microscopy （AFM）. Furthermore, this inorganic/organic hybrid material, SiOE-P（MMA-b-C6SA）, showed excellent thermal stability,tested by TGA measurements. Water and n-hexadecane contact angles on the hybrid surface were both larger than that of the pure fluorinated polymer P（MMA-b-C6SA） surface,which can impart the surface with olephobiity and water-repellence properties. More importantly, this inorganic/organic hybrid surface showed excellent self-cleaning properties, dust can be easily washed away by water or swept away by wind. According to the present study,it is reasonable to predict that the organic-inorganic hybrid coating will be a prospective anti-icing and self-cleaning candidate.

关 键 词：ARGET ATRP 有机无机复合材料 含氟嵌段共聚物 表面引发 自清洁 

分 类 号：O631[理学—高分子化学]