Ringstrand Bryan S, Seifert Sönke, Podlesak David W, Firestone Millicent A
Los Alamos National Laboratory, Los Alamos, NM, 87545, USA.
Argonne National Laboratory, Argonne, IL, 60439, USA.
Macromol Rapid Commun. 2016 Jul;37(14):1155-67. doi: 10.1002/marc.201600070. Epub 2016 May 19.
The UV-initiated free radical polymerization of a lyotropic mesophase prepared by co-assembly of an aqueous mixture of an ionic liquid (IL) monomer, 3-decyl-1-vinylimidazolium chloride, in a dimethyl sulfoxide dispersion of an IL-monomer nanodiamond conjugate yields a well-ordered 2D hexagonally structured network-polymer composite. The IL monomer is covalently bound to carboxylated detonation diamond via ester-linked 3-decyl-1-vinylimidazolium bromide. Successful preparation of the amphiphile-functionalized nanodiamond is determined by ATR/FT-IR, thermogravimetric analysis, and small-angle X-ray scattering (SAXS). Mesophase and composite structure are evaluated by SAXS, revealing a columnar architecture composed of amphiphilic ionic liquid cylinders containing solvent-rich cores. Self-assembly directed site localization of the nanodiamond positions the particles in the alkyl chain continuum upon polymerization. The composite reversibly swells in ethanol allowing structural variation and modulation of the nanoparticle internal packing arrangement. This work demonstrates that through careful molecular design, self-organization and site-directed assembly of nanodiamond into chemically distinct regions of a nanostructured organogel can be achieved.
通过将离子液体（IL）单体3-癸基-1-乙烯基咪唑鎓氯化物的水性混合物与IL-单体纳米金刚石共轭物在二甲基亚砜分散体中进行共组装而制备的溶致液晶相的紫外线引发自由基聚合，产生了一种有序的二维六边形结构的网络聚合物复合材料。IL单体通过酯连接的3-癸基-1-乙烯基咪唑鎓溴与羧化爆轰金刚石共价结合。通过ATR/FT-IR、热重分析和小角X射线散射（SAXS）确定两亲功能化纳米金刚石的成功制备。通过SAXS评估液晶相和复合材料结构，揭示了由含有富溶剂核的两亲性离子液体圆柱体组成的柱状结构。纳米金刚石的自组装定向位点定位在聚合时将颗粒定位在烷基链连续体中。该复合材料在乙醇中可逆膨胀，允许纳米颗粒内部堆积排列的结构变化和调节。这项工作表明，通过精心的分子设计，可以实现纳米金刚石在纳米结构有机凝胶的化学不同区域中的自组织和位点定向组装。
