Choi Francis, Nirmal Ghata, Pizzardi Monica, Acosta Edgar J
Department of Chemical Engineering and Applied Chemistry , University of Toronto , Toronto M5S3E5 , Ontario , Canada.
Langmuir. 2019 Dec 24;35(51):16821-16834. doi: 10.1021/acs.langmuir.9b02822. Epub 2019 Dec 9.
Nanostructured polymers contain features smaller than 100 nm that are useful in a wide range of areas, including photonics, biomedical materials, and environmental applications. Out of the myriad of nanostructured polymers, surfactant-templated polymers are versatile because of their ability to have tunable domain sizes, structure, and composition. This work addresses the gap between the formulation with industrial-grade polymerizable surfactants and the final structure of the polymer, using the hydrophilic-lipophilic difference (HLD) and net-average curvature (NAC) frameworks. HLD indicates the proximity of the formulation (surfactant and oil monomer selection, temperature, electrolyte concentration) to the phase inversion point, where HLD = 0. NAC uses the HLD to determine the curvature of the surfactant-oil-water interface, leading not only to the size and shape of micelles and bicontinuous isotropic (L) systems but also to defining the most likely regions for lyotropic liquid crystal (LLC) existence and phase separation in ternary phase diagrams. Polymerizing LLC fluids produced nanostructured polymers with similar LLC structures that were highly swellable, but with low compressive strength. Polymerizing L fluids produced strong, but less water-swellable nanostructured polymers with a similar characteristic length to the parent L microemulsion. The relatively small scale of the parent LLC (∼6-8 nm) or L (∼3-4 nm) systems is consistent with the translucent nature of the polymers produced and the HLD-NAC predicted sizes.
纳米结构聚合物包含尺寸小于100纳米的特征,这些特征在广泛的领域中都很有用,包括光子学、生物医学材料和环境应用。在众多纳米结构聚合物中,表面活性剂模板聚合物具有通用性,因为它们能够具有可调节的畴尺寸、结构和组成。这项工作利用亲水亲油差(HLD)和净平均曲率(NAC)框架,解决了工业级可聚合表面活性剂配方与聚合物最终结构之间的差距。HLD表示配方(表面活性剂和油单体的选择、温度、电解质浓度)与相转变点的接近程度,其中HLD = 0。NAC利用HLD来确定表面活性剂-油-水界面的曲率,这不仅决定了胶束和双连续各向同性(L)体系的大小和形状,还定义了溶致液晶(LLC)存在和三元相图中相分离的最可能区域。聚合LLC流体产生了具有相似LLC结构的纳米结构聚合物,这些聚合物具有高膨胀性,但抗压强度低。聚合L流体产生了强度高但水膨胀性较低的纳米结构聚合物,其特征长度与母体L微乳液相似。母体LLC(约6 - 8纳米)或L(约3 - 4纳米)体系相对较小的尺度与所生产聚合物的半透明性质以及HLD - NAC预测的尺寸一致。