Polymer blend-filled nanoparticle films via monomer-driven infiltration of polymer and photopolymerization
Polymer blend-filled nanoparticle films via monomer-driven infiltration of polymer and photopolymerization
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DOI：
10.1039/c7me00099e
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发表时间：
2018-02
影响因子：
3.3
通讯作者：
Yiwei Qiang;N. Manohar;K. Stebe;Daeyeon Lee
中科院分区：
文献类型：
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作者：
Yiwei Qiang;N. Manohar;K. Stebe;Daeyeon Lee
在聚合物共混膜中加入纳米颗粒可以产生性能和功能的协同组合。然而，通过传统的熔融或溶液混合技术将大量纳米颗粒添加到聚合物共混基质中，由于颗粒容易聚集，因此具有挑战性。在这里，我们报道了一种直接的方法来制备聚合物共混物/纳米粒子三元复合膜，基于单体驱动的聚合物渗透和光聚合，具有极高的纳米粒子负载。该制备过程包括三个步骤：(1)在聚合物层上制备具有纳米颗粒(NP)层的双层膜；(2)用单体和光引发剂的蒸气混合物对双层膜进行热处理，该双层膜经历毛细管缩合并赋予聚合物层迁移率；(3)将该薄膜暴露在紫外光下以诱导单体的光聚合。该方法中使用的单体在化学上不同于双层中聚合物的重复单元，是聚合物的良好溶剂。第二步导致塑化聚合物的渗透，第三步导致两种聚合物在纳米粒子层的空隙中混合。通过改变初始双层中聚合物层和纳米颗粒层的厚度比以及改变紫外光照射时间，可以调节两种聚合物在复合膜中的体积分数。这种多才多艺的方法使得设计和制造新型纳米复合膜成为可能，这种纳米复合膜在纳米颗粒膜的空隙中包含两种聚合物的纳米级混合，这可能具有独特的机械和传输性能的组合，适合于膜分离、导电复合膜和太阳能电池等高级应用。此外，这些聚合物共混物填充的纳米颗粒膜可以作为模型系统来研究限制对聚合物共混物的相容和形态的影响。
Incorporation of nanoparticles into polymer blend films can lead to a synergistic combination of properties and functionalities. Adding a large concentration of nanoparticles into a polymer blend matrix via conventional melting or solution blending techniques, however, is challenging due to the tendency of particles to aggregate. Herein, we report a straightforward approach to generate polymer blend/nanoparticle ternary composite films with extremely high loadings of nanoparticles based on monomer-driven infiltration of polymer and photopolymerization. The fabrication process consists of three steps: (1) preparing a bilayer with a nanoparticle (NP) layer atop a polymer layer, (2) annealing of the bilayer with a vapour mixture of a monomer and a photoinitiator, which undergoes capillary condensation and imparts mobility to the polymer layer and (3) exposing this film to UV light to induce photopolymerization of the monomer. The monomer used in this process is chemically different from the repeat unit of the polymer in the bilayer and is a good solvent for the polymer. The second step leads to the infiltration of the plasticized polymer, and the third step results in a blend of two polymers in the interstices of the nanoparticle layer. By varying the thickness ratio of the polymer and nanoparticle layers in the initial bilayers and changing the UV exposure duration, the volume fraction of the two polymers in the composite films can be adjusted. This versatile approach enables the design and engineering of a new class of nanocomposite films that contain a nanoscale-blend of two polymers in the interstices of a nanoparticle film, which could have combinations of unique mechanical and transport properties desirable for advanced applications such as membrane separations, conductive composite films and solar cells. Moreover, these polymer blend-filled nanoparticle films could serve as model systems to study the effect of confinement on the miscibility and morphology of polymer blends.