Zhao Zhengbai, Xie Haijiao, An Shuangshuang, Jiang Yong
School of Chemistry and Chemical Engineering, Southeast University , Jiangning, Nanjing, Jiangsu 211189, P. R. China.
J Phys Chem B. 2014 Dec 18;118(50):14640-7. doi: 10.1021/jp507682k. Epub 2014 Dec 9.
In this article, the multicomponent copolymers were prepared by the copolymerization of two hydrophobic silicon-containing monomers bis(trimethylsilyloxy) methylsilylpropyl glycerol methacrylate (SiMA) and tris(trimethylsiloxy)-3-methacryloxypropylsilane (TRIS) with three hydrophilic monomers 2-hydroxyethyl methacrylate, N-vinylpyrrolidone, and N,N-dimethyl acrylamide. The copolymers were hydrated to form transparent silicone hydrogels. The oxygen permeability coefficients (Dk) of hydrogels were measured, and their relationships with the equilibrium water contents (EWC) and the types and contents of silicon containing monomers as well as the phase separation structures of silicone hydrogels were analyzed in detail. The results showed that the EWC decreased as the increase of SiMA content. The relationship between Dk and SiMA content, as well as that between Dk and EWC, showed inverted bell curve distributions, which meant two main factors, i.e., silicon-oxygen bond in silicone and water in hydrogel, contributed to oxygen permeation and followed a mutual inhibition competition mechanism. The internal morphologies of the hydrogels were observed by transmission electron microscope, and the results showed that the hydrogels presented two different phase separation structures depending on the types of the silicon-containing monomers. The silicone phase in SiMA containing hydrogel presented to be a granular texture, while the silicone phase in TRIS containing hydrogel formed a fibrous texture which resulted in a higher Dk value. These results could help to design a silicone hydrogel with better properties and wider application.
在本文中,通过两种含硅疏水单体甲基丙烯酸双(三甲基硅氧基)甲基硅丙基甘油酯(SiMA)和三(三甲基硅氧基)-3-甲基丙烯酰氧基丙基硅烷(TRIS)与三种亲水单体甲基丙烯酸2-羟乙酯、N-乙烯基吡咯烷酮和N,N-二甲基丙烯酰胺的共聚反应制备了多组分共聚物。将共聚物水合形成透明的硅水凝胶。测量了水凝胶的透氧系数(Dk),并详细分析了它们与平衡含水量(EWC)、含硅单体的类型和含量以及硅水凝胶的相分离结构之间的关系。结果表明,随着SiMA含量的增加,EWC降低。Dk与SiMA含量之间的关系以及Dk与EWC之间的关系呈现倒钟形曲线分布,这意味着两个主要因素,即硅氧烷中的硅氧键和水凝胶中的水,对氧气渗透有贡献,并遵循相互抑制竞争机制。通过透射电子显微镜观察了水凝胶的内部形态,结果表明,根据含硅单体的类型,水凝胶呈现出两种不同的相分离结构。含SiMA的水凝胶中的硅氧烷相呈现颗粒状纹理,而含TRIS的水凝胶中的硅氧烷相形成纤维状纹理,这导致了更高的Dk值。这些结果有助于设计具有更好性能和更广泛应用的硅水凝胶。