Continuous synthesis of block copolymer nanoparticles via telescoped RAFT solution and dispersion polymerisation in a miniature CSTR cascade
Continuous synthesis of block copolymer nanoparticles via telescoped RAFT solution and dispersion polymerisation in a miniature CSTR cascade
复制标题
通过伸缩 RAFT 溶液和微型 CSTR 级联中的分散聚合连续合成嵌段共聚物纳米颗粒
DOI：
10.1039/d2re00475e
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发表时间：
2023
影响因子：
3.9
通讯作者：
Pittaway P
中科院分区：
文献类型：
--
作者：
Pittaway P
微型连续流反应器为探索高价值化学产品的合成提供了一条安全、经济和可扩展的路线。在聚合物合成的背景下，精确限定和可调节的产物可以通过可逆失活自由基聚合（RDRP）技术制备，例如可逆加成-断裂链转移（RAFT），通常报道管式反应器。在此，我们提出了一个微型连续搅拌釜式反应器（CSTR）级联连续流RAFT聚合与积极的混合，这是发现执行接近的理论CSTR级联在这项研究中考虑的聚合。的反应器的性能进行了评估，为N，N-二甲基丙烯酰胺（DMAm）的水溶液RAFT聚合和RAFT分散聚合的双丙酮丙烯酰胺使用聚（DMAm）的大分子链转移剂（macro-CTA）。已确定停留时间分布（RTD）对于告知所得聚合物的性质是重要的，更多的CSTR导致更窄的摩尔质量分布。对于通过聚合诱导的自组装（比萨）的颗粒合成，在单独的分批和流动实验中制备一系列嵌段共聚物，尽管分子量相当，但发现所获得的颗粒不同。为了开发高通量筛选平台，将多级、伸缩式管式-CSTR级联反应器配置应用于在线大分子CTA合成和随后的嵌段扩展。所使用的加工方法之间的产品特性差异支持聚合物是所谓的“过程产品”的想法;实际上，通过应用替代合成方法，可以从相同的化学过程中获得不同的聚合物产品。
Miniaturised continuous-flow reactors offer a safe, economical, and scalable route to explore the synthesis of high-value chemical products. In the context of polymer synthesis, precisely defined and tuneable products can be prepared via reversible de-activation radical polymerisation (RDRP) techniques such as reversible addition-fragmentation chain-transfer (RAFT), for which tubular reactors are commonly reported. Herein, we present a miniature continuous stirred-tank reactor (CSTR) cascade for continuous-flow RAFT polymerisation with active mixing throughout, which is found to perform close to a theoretical CSTR cascade for the polymerisations considered in this study. The performance of the reactor is evaluated for both the aqueous solution RAFT polymerisation of N,N-dimethylacrylamide (DMAm) and the RAFT dispersion polymerisation of diacetone acrylamide using a poly(DMAm) macromolecular chain transfer agent (macro-CTA). It was determined that the residence time distribution (RTD) is important for informing the properties of the resulting polymers, with more CSTRs resulting in a narrower molar mass distribution. For particle synthesis by polymerisation-induced self-assembly (PISA), a series of block copolymers were prepared in separate batch and flow experiments for which the particles obtained were found to vary despite comparable molecular weights. Towards the development of a high throughput screening platform, a multi-stage, telescoped tubular-CSTR cascade reactor configuration was applied for inline macro-CTA synthesis and subsequent block extension. Differences in product properties between the processing methods used supports the idea that polymers are so-called ‘products-by-process’; indeed different polymer products can be accessed from the same chemistry through the application of alternative synthesis approaches.