POSS基杂化含氟丙烯酸酯共聚物涂膜的表面相分离与疏水性研究

发布时间：2018-06-01 10:36

本文选题：POSS + 含氟丙烯酸酯聚合物　；参考：《高分子学报》2017年04期

【摘要】：采用自由基溶液聚合法成功合成了多面体低聚倍半硅氧烷(POSS)基杂化含氟丙烯酸酯共聚物,并采用核磁共振仪(NMR)和凝胶渗透色谱仪(GPC)表征了共聚物,其中POSS和含氟单体分步加入到反应中.首先将共聚物溶解到三氟三氯乙烷(F113)和乙酸乙酯的混合溶剂中配制成溶液,然后通过直接在玻璃片上滴落共聚物溶液制备了共聚物涂膜.采用扫描电子显微镜(SEM)、X-射线光电子能谱(XPS)、原子力显微镜(AFM)和接触角测量仪考察了F113和乙酸乙酯的配比对共聚物涂膜表面形貌、表面元素组成、表面粗糙度以及表面疏水性的影响.实验数据表明POSS在表面能够聚集成纳米颗粒并能极大增强涂膜表面粗糙度和疏水性.共聚物表面同时存在POSS聚集与有机相微相分离两类相分离行为,并形成了复合粗糙结构.虽然POSS和含氟段竞争迁移到表面,但是随着混合溶剂中F113的增多,涂膜表面含氟量越来越多,同时POSS在表面的聚集体越来越少,表面平均粗糙度越来越小,最终涂膜的疏水性越来越强,这说明F113有助于提升氟的趋表迁移能力,使涂膜表面含氟链段占据较多的表面空间,从而抑制了POSS在表面聚集分布.当使用纯F113作为溶剂时,共聚物涂膜的表面氟含量为45.25%,平均粗糙度为93.4 nm,此时静态水接触角最大为135.0?,表现出优异的疏水性.
[Abstract]:Polyhedron oligosilane oligomer POSS-based hybrid fluorinated acrylate copolymers were synthesized by free radical solution polymerization. The copolymers were characterized by nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). POSS and fluorine monomer were added into the reaction step by step. The copolymers were first dissolved in the mixed solvent of Trifluorotrichloroethane (F113) and ethyl acetate, and then the copolymers film was prepared by dropping the copolymers directly on the glass sheets. The surface morphology and elemental composition of copolymers coated with F113 and ethyl acetate were investigated by means of scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) and contact angle measuring instrument. The influence of surface roughness and hydrophobicity. Experimental data show that POSS can aggregate into nanoparticles on the surface and greatly enhance the surface roughness and hydrophobicity of the film. There are two kinds of phase separation behaviors on the surface of the copolymer: POSS aggregation and organic phase separation, and the composite rough structure is formed. Although the POSS and fluorine segments migrate to the surface in competition, with the increase of F113 in the mixed solvent, the fluorine content on the surface of the coating film becomes more and more, at the same time, the aggregation of POSS on the surface is less and less, and the average roughness of the surface is becoming smaller and smaller. Finally, the hydrophobicity of the film becomes stronger and stronger, which indicates that F113 can improve the mobility of fluorine, and make the fluorine chain segment occupy more surface space on the surface of the coating film, thus inhibiting the aggregation and distribution of POSS on the surface. When pure F113 was used as solvent, the surface fluorine content of the copolymer film was 45.25, the average roughness was 93.4 nm, and the static water contact angle was 135.0%, showing excellent hydrophobicity.
【作者单位】：华南理工大学化学与化工学院;
【基金】：国家自然科学基金(基金号21176091,21376093) 广州市科技计划项目(项目号201607010172)资助
【分类号】：TB306

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