瓶刷状聚合物作为模板负载功能物质得到复合功能结构的方法显示了巨大潜力，合成棒、椭球、环等精细纳米结构及构建其功能性超结构具有重要意义。由于分子间反应在模板固化过程中的存在，传统方法无法在高浓度下合成此类纳米结构。本研究基于瓶刷状聚合物静电介导分子内交联方法，实现Janus纳米棒、Janus纳米椭球、纳米环的规模合成，为进一步组装提供关键基元。代表结果如下： 1、提出了AB型活性Janus纳米棒的合成方法。通过活性阳离子聚合主链接枝活性阴离子聚合链的方式，制备了Janus瓶刷状聚合物模板。基于静电介导分子内交联方法实现固化获得Janus纳米棒，最高浓度可达300 mg/mL。Janus纳米棒的组成和尺寸可控，两端的保护基团经活化后可衍生AB型活性Janus纳米棒，活性基团可负载荧光染料实现标记，为其荧光显微观察提供保证。 2、活性Janus纳米棒两端的羧基和氨基数量可控，为调控其自组装结构提供基础。随官能团数目增加，可以形成线型、分支型和3D网络型组装体结构。纳米棒线可通过超声断裂，为二次组装提供新单元。以交联聚合物纳米棒为模板，通过表面复合与煅烧可合成纳米管，其组成与特征尺寸可控。 3、调节瓶刷状聚合物主链和支链长度，实现Janus纳米棒向Janus纳米椭球的转变。Janus纳米椭球的最高合成浓度可达150 mg/mL。负载四氧化三铁赋予纳米椭球顺磁性。可通过表面溶胶-凝胶反应引入二氧化硅并为进一步改造提供条件。可在椭球表面定量引入第三根和第四根活性聚合物链，获得更丰富的复合纳米颗粒结构。 4、以两端含有双键的A2型瓶刷状聚合物模板为原料，通过分子内成环反应可合成纳米环。提出了静电介导-微相聚集协调成环方法，最高成环反应浓度可达80 mg/mL，产物纯净。纳米环组成和尺寸可控，为研究环的本征性质及功能耦合提供了关键材料。
Derivation of polymer bottlebrushes toward composite functional structures has shown vast potential. Synthesis of fine nanostructures including rods, ellipsoids, rings and further functional superstructures has significant implications. Large-scale synthesis of aforementioned nanostructures is greatly hampered by intermolecular reaction during solidification. This dissertation focuses on methodological development to large-scale synthesize polymer bottlebrushes derived functional nanocomposites based on our previously reported electrostatics-mediated intramolecular crosslinking method. The derived nanocomposites serve as key monomers in assembly. The representative results are as follows. 1. AB-type reactive Janus nanorods with two different functional groups at the opposite ends were effectively synthesized. The parent polymer bottlebrush was synthesized by living cationic polymerization and further grafting of the living anionic polymer chains. Based on the electrostatics-mediated intramolecular crosslinking, the Janus nanorods could be synthesized at an unprecedentedly high concentration of 300 mg/mL. Both composition and characteristic size of the Janus nanorods were greatly tunable. The protected groups at the opposite ends of the nanorod could be activated orthogonally to derive the reactive AB-type Janus nanorods. Fluorescence labelling of the groups allowed easy visualization of the Janus nanorods under microscope. 2. The reactive Janus nanorods could self-assemble into various superstructures depending on the number of carboxyl and amino groups at the Janus nanorods. Linear chain, branched structure, and 3D network were thus achieved. The nanorods could be broken into shorter ones under ultrasonication, which could derive a series of secondary assembly structures. Nanotubes of tunable composition and size could be synthesized by coating and calcination of crosslinked polymer nanorods. 3. The reactive Janus nanorods could become ellipsoids when the main chain was short and the side chain was long. Janus ellipsoids could be synthesized at 150 mg/mL. The ellipsoid became superparamagnetic upon loading ferrosoferric oxide. A thin layer of silica was coated at the ellipsoid by sol-gel process facilitating further functionalizations. Other two chains could be readily grafted at the ellipsoid by the termination approach. The ellipsoids with varied composition and nanostructure provide a powerful tool to achieve superstructures. 4. Polymer nanoring structures could be synthesized via intramolecular cyclization of A2-type bottlebrush polymers with vinyl groups at both ends. Based on electrostatics-mediated microphase-coordinated intramolecular cyclization method, the cyclization could be performed at 80 mg/mL to achieve pure polymer rings. Both composition and characteristic size of the rings were tunable. This novel method provides materials for the research on the intrinsic properties and functional coupling of nano rings.
