Ernst-Berl-Institute for Chemical Engineering and Macromolecular Science, Technische Universität Darmstadt , Alarich-Weiss-Str. 4, D-64287 Darmstadt, Germany.
Surface Science Group, Institute of Materials Science, Technische Universität Darmstadt , Otto-Berndt-Str. 3, D-64287 Darmstadt, Germany.
ACS Appl Mater Interfaces. 2018 Jan 31;10(4):4018-4030. doi: 10.1021/acsami.7b18014. Epub 2018 Jan 18.
Metallopolymers are a unique class of functional materials because of their redox-mediated optoelectronic and catalytic switching capabilities and, as recently shown, their outstanding structure formation and separation capabilities. Within the present study, (tri)block copolymers of poly(isoprene) (PI) and poly(ferrocenylmethyl methacrylate) having different block compositions and overall molar masses up to 328 kg mol are synthesized by anionic polymerization. The composition and thermal properties of the metallopolymers are investigated by state-of-the-art polymer analytical methods comprising size exclusion chromatography, H NMR spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. As a focus of this work, excellent microphase separation of the synthesized (tri)block copolymers is proven by transmission electron microscopy, scanning electron microcopy, energy-dispersive X-ray spectroscopy, small-angle X-ray scattering measurements showing spherical, cylindrical, and lamellae morphologies. As a highlight, the PI domains are subjected to ozonolysis for selective domain removal while maintaining the block copolymer morphology. In addition, the novel metalloblock copolymers can undergo microphase separation on cellulose-based substrates, again preserving the domain order after ozonolysis. The resulting nanoporous structures reveal an intriguing switching capability after oxidation, which is of interest for controlling the size and polarity of the nanoporous architecture.
金属聚合物因其氧化还原介导的光电和催化开关性能而成为一类独特的功能材料，并且最近的研究表明，它们还具有出色的结构形成和分离能力。在本研究中，通过阴离子聚合合成了具有不同嵌段组成和高达 328kg/mol 的总摩尔质量的聚异戊二烯（PI）和聚二茂铁基甲基丙烯酸甲酯（PFMA）的（三）嵌段共聚物。通过包括尺寸排阻色谱、H NMR 光谱、差示扫描量热法和热重分析在内的最先进的聚合物分析方法研究了金属聚合物的组成和热性能。作为这项工作的重点，通过透射电子显微镜、扫描电子显微镜、能量色散 X 射线光谱、小角 X 射线散射测量证明了合成的（三）嵌段共聚物具有出色的微相分离，显示出球形、圆柱和层状形态。值得一提的是，PI 域经历臭氧氧化以选择性地去除域，同时保持嵌段共聚物形态。此外，新型金属嵌段共聚物可以在基于纤维素的基底上进行微相分离，并且在臭氧氧化后仍保持域序。所得的纳米多孔结构在氧化后表现出有趣的开关性能，这对于控制纳米多孔结构的尺寸和极性具有重要意义。
