Tunable Fluorophobic Effect Determines Nanoparticle Dispersion in Homopolymers and Block Polymers
Tunable Fluorophobic Effect Determines Nanoparticle Dispersion in Homopolymers and Block Polymers
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DOI：
10.1002/admi.201901691
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发表时间：
2019-12
影响因子：
5.4
通讯作者：
Zachary M. Marsh;D. Blom;M. Stefik
中科院分区：
文献类型：
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作者：
Zachary M. Marsh;D. Blom;M. Stefik
纳米粒子（NPs）在均聚物和嵌段聚合物中的受控放置对于功能性纳米材料具有广泛的意义。这篇手稿重点关注小分子稳定的NP，这些NP带来了很大一部分功能。对于这种NP与嵌段聚合物的混合物，迄今为止压倒性的焦点是使用有吸引力的相互作用将亲水性NP定位在嵌段聚合物的亲水性部分内。相关的亲脂性方法通常将NP置于嵌段聚合物界面处。在这里，开发了一种用于嵌段聚合物-NP控制的新模式，其相当依赖于经由疏氟效应的排斥。氟化物质通过来自非氟化介质的排斥而强烈缔合。在这里，氟化NP与配体混合物一起制成，用于对疏氟效应的强度进行颗粒控制。小角X射线散射数据显示，所有F-NP都容易与聚苯乙烯相分离，而增加疏氟强度使得能够在氟化均聚物内分散。接下来，研究了F-NP在二嵌段聚合物内的放置作为疏氟强度的函数。发现弱疏氟F-NP主要在二嵌段界面附近，而发现强疏氟F-NP分散在整个氟化嵌段中。纳米粒子的受控放置是一种新兴的自组装材料的方法。
The controlled placement of nanoparticles (NPs) within homopolymers and block polymers is of broad interest for functional nanomaterials. This manuscript focuses on small molecule‐stabilized NPs that bring a large fraction of functionality. For such NP mixtures with block polymers, the overwhelming focus to date has been the use of attractive interactions to localize hydrophilic NPs within the hydrophilic portion of block polymers. Related lipophilic approaches often place NPs at the block polymer interface. Here, a new modality for block polymer–NP control is developed that rather relies upon repulsion via the fluorophobic effect. Fluorinated species strongly associate via repulsion from nonfluorinated media. Here, fluorinated NPs are made with ligand mixtures for granular control over the strength of the fluorophobic effect. Small‐angle X‐ray scattering data reveal that all F‐NPs readily phase separate from polystyrene whereas increasing fluorophobic strength enables dispersions within a fluorinated homopolymer. Next, the F‐NP placement within diblock polymers is investigated as a function of the fluorophobic strength. Weakly fluorophobic F‐NPs are found predominantly near the diblock interface whereas strongly fluorophobic F‐NPs are found to disperse throughout the fluorinated block. The controlled placement of NPs is an emerging way to self‐assemble materials.