School of Engineering Technology and Coatings Research Institute, Eastern Michigan University , Ypsilanti, Michigan 48197, United States.
Langmuir. 2013 Sep 24;29(38):12013-24. doi: 10.1021/la402331b. Epub 2013 Sep 11.
A polymerizable ionic liquid surfactant, 1-(11-acryloyloxyundecyl)-3-methylimidiazolium bromide (ILBr), was copolymerized with methyl methacrylate (MMA) in aqueous microemulsions at 30% (ILBr w/w) and various water to MMA ratios. The ternary phase diagram of the ILBr/MMA/water system was constructed at 25 and 60 °C. Homopolymers and copolymers of ILBr and MMA were produced by thermally initiated chain radical microemulsion polymerization at various compositions in bicontinuous and reverse microemulsion subdomains. Microemulsion polymerization reaction products varied from being gel-like to solid, and these materials were analyzed by thermal and scanning electron microscopy methods. Microemulsion polymerized materials were insoluble in all solvents tested, consistent with light cross-linking. Ion exchange between Br(-) and PF6(-) in these copolymeric materials resulted in the formation of open-cell porous structures in some of these materials, as was confirmed by scanning electron microscopy (SEM). Several compositions illustrate the capture of prepolymerization nanoscale structure by thermally initiated polymerization, expanding the domain of compositions exhibiting this feat and yet to be demonstrated in any other system. Regular cylindrical pores in interpenetrating ILBr-co-MMA and PMMA networks are produced by anion exchange in the absence of templates. A percolating cluster/bicontinuous transition is "captured" by SEM after using anion exchange to visualize the mixed cluster/pore morphology. Some design principles for achieving this capture and for obtaining stimuli responsive solvogels are articulated, and the importance of producing solvogels in capturing the nanoscale is highlighted.
一种可聚合的离子液体表面活性剂 1-(11-丙烯酰氧基十一烷基)-3-甲基咪唑溴盐（ILBr）与甲基丙烯酸甲酯（MMA）在 30%（ILBr w/w）和各种水与 MMA 比例的水微乳液中共聚。在 25 和 60°C 下构建了 ILBr/MMA/水体系的三元相图。ILBr 和 MMA 的均聚物和共聚物通过在各种组成的双连续和反相微乳液亚相中通过热引发链自由基微乳液聚合来制备。微乳液聚合反应产物从凝胶状变为固体状，通过热和扫描电子显微镜方法对这些材料进行了分析。微乳液聚合的材料在所有测试的溶剂中都不溶，与轻度交联一致。这些共聚物材料中的 Br(-)和 PF6(-)之间的离子交换导致其中一些材料形成开孔多孔结构，这通过扫描电子显微镜（SEM）得到证实。一些组成部分说明了预聚合纳米结构通过热引发聚合被捕获，扩展了表现出这种特性的组成部分的范围，而这在任何其他系统中都尚未得到证明。在没有模板的情况下，通过阴离子交换在互穿的 ILBr-co-MMA 和 PMMA 网络中产生规则的圆柱形孔。通过阴离子交换来可视化混合簇/孔形态，“捕获”了渗透簇/双连续转变的 SEM。阐述了实现这种捕获和获得刺激响应溶剂凝胶的一些设计原则，并强调了在捕获纳米尺度时产生溶剂凝胶的重要性。
