Phosphonic Acid-Functionalized Diblock Copolymer Nano-Objects via Polymerization-Induced Self-Assembly: Synthesis, Characterization, and Occlusion into Calcite Crystals
Phosphonic Acid-Functionalized Diblock Copolymer Nano-Objects via Polymerization-Induced Self-Assembly: Synthesis, Characterization, and Occlusion into Calcite Crystals
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DOI：
10.1021/acs.macromol.5b02212
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发表时间：
2016-01-12
期刊：
影响因子：
5.5
通讯作者：
Armes, Steven P.
中科院分区：
文献类型：
--
作者：
Hanisch, Andreas;Yang, Pengcheng;Armes, Steven P.
采用二烷基膦酸功能化和膦酸功能化大分子链转移剂（macro- cta）在64℃的甲醇中以20% w/w的固体浓度进行了甲基丙烯酸苄酯（BzMA）的可逆加成-破碎链转移（RAFT）分散聚合。当使用相对较短的macrocta时，通过改变成核PBzMA块的平均聚合度，可以分别生成泡状纳米物体。详细的相图的构建对于纯共聚物形态的可重复性定位至关重要，这些共聚物形态使用透射电子显微镜（TEM）和动态光散射（DLS）进行了表征。对于使用膦酸基宏观cta制备的纳米物体，从甲醇到水的转移由于稳定剂链的电离而导致阴离子表面电荷的发展，但这不会对共聚物的形态产生不利影响。考虑到磷酸对钙离子的强亲和力，选择的纳米物体在生长的CaCO3晶体中进行原位遮挡评估。扫描电子显微镜（SEM）研究为蠕虫状和水泡状膦酸基纳米物体的闭合提供了令人信服的证据，从而产生了一系列有趣的新型有机-无机纳米复合材料。
Dialkylphosphonate-functionalized and phosphonic acid-functionalized macromolecular chain transfer agents (macro-CTAs) are utilized for the reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization of benzyl methacrylate (BzMA) at 20% w/w solids in methanol at 64 degrees C. Spherical, worm-like, and vesicular nano-objects could each be generated through systematic variation of the mean degree of polymerization of the core-forming PBzMA block when using relatively short macroCTAs. Construction of detailed phase diagrams is essential for the reproducible targeting of pure copolymer morphologies, which were characterized using transmission electron microscopy (TEM) and dynamic light scattering (DLS). For nano-objects prepared using the phosphonic acid-based macro-CTA, transfer from methanol to water leads to the development of anionic surface charge as a result of ionization of the stabilizer chains, but this does not adversely affect the copolymer morphology. Given the well-known strong affinity of phosphonic acid for calcium ions, selected nano-objects were evaluated for their in situ occlusion within growing CaCO3 crystals. Scanning electron microscopy (SEM) studies provide compelling evidence for the occlusion of both worm-like and vesicular phosphonic acid-based nano-objects and hence the production of a series of interesting new organic-inorganic nanocomposites.