Continuous-flow Synthesis of Functional Polymeric Materials

近年来，连续流化学已成为多步合成多种有机化合物的有力技术。它可以提供一种更快、更清洁、更便宜的有机合成手段，而复杂的、多步骤的合成可以通过中间体的快速进展而串联进行，收率相对较高。目前，大多数工业规模的聚合物合成都是使用间歇式技术进行的，这种技术存在一些固有的缺点，例如需要处理大量的潜在危险化学品，传热差，以及当批次失败时产生大量的废料。该项目的目的是设计连续流系统，该系统针对一系列聚合物材料的合成进行了优化。一系列完善的可控聚合技术，如可逆加成断裂链转移（RAFT）聚合和原子转移自由基聚合（ATRP），将被用于合成各种可控结构聚合物和响应性聚合物纳米颗粒。流动系统的独特性质将被利用，以实现对聚合物链结构的更好控制。例如，通过精确的温度控制来降低分子量分布；通过简单地改变流速来微调聚合物链的分子量；并对序贯加成法合成多嵌段共聚物进行了研究。此外，随后的嵌段共聚物自组装和封装将陆续尝试。所得到的聚合物和颗粒将使用一系列分析技术进行全面表征，包括核磁共振波谱、凝胶渗透色谱（GPC）、动态光散射和电子显微镜。在合成过程中也可能有机会开发在线分析，以理解和进一步优化这种连续流过程（例如在线GPC）。这种精确的控制将允许可靠和可重复的聚合物系统的制备，具有可调的性能和潜在的应用在医疗保健，个人护理，汽车和农用化学工业。此外，更好的传热和减少的废物可以减少能源消耗、排放和运行成本。

In recent years, the field of continuous flow chemistry has become a powerful technique for multi-step synthesis of a wide range of organic compounds. It can provide a faster, cleaner and cheaper means of organic synthesis, while complex, multi-step syntheses can be conducted in series with relatively high yields through the rapid progression of intermediates. At present, most industrial scale polymer synthesis is carried out using batch techniques, which have some inherent disadvantages, such as the requirement to deal with large volumes of potentially hazardous chemicals, poor heat transfer and large volumes of waste material when batches fail. The aim of this project is to design continuous-flow systems, which are optimised for the synthesis of a range of polymeric materials. A range of well established, controlled polymerisation techniques such as reversible addition fragmentation chain transfer (RAFT) polymerisation and atom transfer radical polymerisation (ATRP) will be used will be used to synthesise various controlled structure polymers and responsive polymer nanoparticles. The unique properties of flow systems will be exploited in order to achieve finer control over the architecture of the polymer chains. For example, reducing the molecular weight distributions using precise temperature control; fine tuning the molecular weights of polymer chains by simply altering flow rates; and the synthesis of multi-block copolymers by sequential monomer addition will be investigated. Furthermore, subsequent block copolymer self-assembly and encapsulation will be attempted in series.The resulting polymers and particles will be fully characterised using a range of analytical techniques including NMR spectroscopy, gel permeation chromatography (GPC), dynamic light scattering and electron microscopy. There may also be opportunities for developing on-line analysis during the synthesis in order to understand and further optimise such continuous-flow processes (e.g. On-line GPC). Such accurate control will allow for reliable and reproducible preparation of polymeric systems with tuneable properties and potential applications in the healthcare, personal care, automotive and agrochemical industries. Furthermore, better heat transfer and reduced waste products allow a reduction in energy consumption, emissions and running costs.