Kepczyński Mariusz, Lewandowska Joanna, Romek Marek, Zapotoczny Szczepan, Ganachaud François, Nowakowska Maria
Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków, Poland.
Langmuir. 2007 Jun 19;23(13):7314-20. doi: 10.1021/la063442i. Epub 2007 May 24.
A simple and effective way to synthesize hollow silicone resin particles of controlled diameter is presented. The synthesis utilizes catanionic vesicles as templates for the polycondensation/polymerization processes of 1,3,5,7-tetramethylcyclotetrasiloxane (D4H) within their membranes. Two different surfactant systems were used to form the vesicular templates: mixtures of dodecyltrimethylammonium bromide (DTAB) and sodium dodecylbenzenesulfonate (SDBS) in the cationic (the DTAB/SDBS system) or anionic (the SDBS/DTAB system) rich region of the phase diagram. The templates obtained from these surfactant mixtures form spontaneously unilamellar vesicles in aqueous solution. The vesicular templates swell upon addition of D4H, thus increasing their size. The silicone resin was obtained in acid- or base-catalyzed polycondensation and ring-opening polymerization processes of D4H. In the case of the DTAB/SDBS system the formation of a densely cross-linked silicone material with SiO3/2 units allowed the nanocapsules to retain the vesicular shape after removal of the template, whereas in the SDBS/DTAB system, the polymer produces capsules which are too smooth to support surfactant lysis. The morphology of the silicone nanocapsules was analyzed using transmission electron microscopy (TEM) and, in some cases, atomic force microscopy (AFM). TEM and AFM reveal discrete hollow particles with a small amount of linked or aggregated hollow silica shells.
本文提出了一种简单有效的方法来合成直径可控的中空有机硅树脂颗粒。该合成方法利用阴阳离子囊泡作为模板,使1,3,5,7 - 四甲基环四硅氧烷(D4H)在其膜内进行缩聚/聚合过程。使用了两种不同的表面活性剂体系来形成囊泡模板:在相图的阳离子富集区(DTAB/SDBS体系)或阴离子富集区(SDBS/DTAB体系)中,十二烷基三甲基溴化铵(DTAB)和十二烷基苯磺酸钠(SDBS)的混合物。从这些表面活性剂混合物中获得的模板在水溶液中自发形成单层囊泡。加入D4H后,囊泡模板会膨胀,从而增大其尺寸。通过D4H的酸催化或碱催化缩聚以及开环聚合过程获得有机硅树脂。在DTAB/SDBS体系中,形成具有SiO3/2单元的密集交联有机硅材料,使得在去除模板后纳米胶囊能够保持囊泡形状,而在SDBS/DTAB体系中,聚合物产生的胶囊过于光滑,无法支持表面活性剂裂解。使用透射电子显微镜(TEM)对有机硅纳米胶囊的形态进行了分析,在某些情况下还使用了原子力显微镜(AFM)。TEM和AFM显示出离散的中空颗粒,带有少量相连或聚集的中空二氧化硅壳。