Polymer Synthesis in Continuous Flow Reactors

A variety of polymerizations has long been performed in continuous flow reactors on an industrial scale; comparatively, on smaller scales, continuous polymerization methods have only gained significant attention in recent years. Yet, within the last decade, the field has moved from the rare occurrence of flow reactors to their abundant use today. A wide variety of polymer reactions have been performed in a continuous fashion on small and intermediate scales. The advantages of applying flow chemistry principles for polymer reactions include increased reproducibility and synthetic precision, significant increases in reaction performances for photochemical reactions, the ability to couple reactors to create complex materials in a single reactor pass, as well as the unique combination of online monitoring and machine learning. In this review we give a comprehensive overview of polymer reactions being carried out in continuous flow reactors to date. The development of the field is discussed, concluding with the most recent examples on automated polymer synthesis, reactor telescoping and nanoparticle synthesis. Finally, the design of flow reactors is discussed to help newcomers contribute to the current and future developments in the field

Poly(methyl methacrylate)-silica microcapsules by templating Pickering emulsion droplets

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Profluorescent PPV-Based Micellar System as a Versatile Probe for Bioimaging and Drug Delivery

Although micelles are commonly used for drug delivery purposes, their long-term fate is often unknown due to photobleaching of the fluorescent labels or the use of toxic materials. Here, we present a metal-free, nontoxic, nonbleaching, fluorescent micelle that can address these shortcomings. A simple, yet versatile, profluorescent micellar system, built from amphiphilic poly(p-phenylenevinylene) (PPV) block copolymers, for use in drug delivery applications is introduced. Polymer micelles made from PPV show excellent stability for up to 1 year and are successfully loaded with anticancer drugs (curcumin or doxorubicin) without requiring introduction of physical or chemical cross-links. The micelles are taken up efficiently by the cells, which triggers disassembly, releasing the encapsulated material. Disassembly of the micelles and drug release is conveniently monitored as fluorescence of the single polymer chains appear, which enables not only to monitor the release of the payload, but in principle also the fate of the polymer over longer periods of time

Rapid Oxygen Tolerant Aqueous RAFT Photopolymerization in Continuous Flow Reactors

Recently, new controlled polymerization pathways have emerged for the synthesis of functional polymer materials. The use of light, particularly visible light, to generate radicals has shown to be beneficial over thermal induction due to the high control over reaction parameters as well as spatiotemporal control. Although numerous photopolymerizations have been performed in batch, additional initiators or activators are often needed to increase the overall yield, making this process time-consuming and costly; optical path lengths directly correlate with achievable space-time yields. The use of flow reactors is in this case advantageous. In this work, new synthetic protocols are demonstrated for the synthesis of di- and triblock copolymers in tubular reactors via photoinduced electron/energy transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization. Within just 10 min of polymerization time, full monomer conversion was reached for a variety of acrylamides and acrylates, and polymers with molecular weights up to 100000 g mol(-1) and high end-group fidelity were obtained. Changing the flow rates, concentrations, and light intensity allowed alteration of the molecular weights, and several di- and triblock copolymers were synthesized, indicating the high level of control over the polymerization. In addition, multiple flow reactors were coupled to allow the synthesis of triblock copolymers in a reactor cascade process without the need for intermediate purification. The attractiveness of this approach is illustrated by considering that a PDMAA-b-PDMAA-b-PDMAA triblock copolymer with a number-average molecular weight of 3200 g mol(-1) and dispersity of 1.24 could be theoretically obtained at a rate of 300 g/day.MCSC-IF-GF applicant no. 12U1717N. We acknowledge The European Union Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant agreement No. 665501 with the research Foundation Flanders (FWO) (N.Z.)