Polymer Networks as Carrier for Organo Catalysts within Continuously Driven Microfluidic Reactor Systems

• Applicant: Professor Dr. Dirk Kuckling
• Subject Area: Polymer Materials ; Organic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2021 to 2026
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 463498885

• Final Report Year: 2025

Final Report Abstract

Continuous flow reactions using gel-bound organo-catalysts in a microfluidic reactor is an attractive approach in organic synthesis. Here, we have synthesized various catalytic monomers from various functional organo-catalyst and polymerized using photolithography to form polymeric gel dots with different compositions of catalyst, gelling agent and crosslinker. The morphology of the gel dots was evaluated by optical and Laser 3D microscopy. Swelling properties of the gel dots were determined in different reaction solvent mixtures and at different temperatures. The synthesized gel-bounded organocatalysts were inserted into a microfluidic reactor (MFR) and used for conducting different organic reactions like Knoevenagel reaction, Aldol reaction, and Baylis-Hillman reaction under mild conditions. The conversion of the reaction was determined mainly by nuclear magnetic resonance (NMR) as an offline method after collecting elute from the MFR for respective times (less the residence time). Reaction parameters like solvent, flowrate, concentration of reactants, and temperature were optimized. In total reactions could be performed with less catalyst and with similar selectivity as respective batch reactions.

Link to the final report

http://dx.doi.org/10.17619/UNIPB/1-2416

Publications

• Continuous Flow Synthesis of Azoxybenzenes by Reductive Dimerization of Nitrosobenzenes with Gel‐Bound Catalysts. European Journal of Organic Chemistry, 2021(11), 1628-1636.
  Schmiegel, Carsten J.; Berg, Patrik; Obst, Franziska; Schoch, Roland; Appelhans, Dietmar & Kuckling, Dirk
  
• Direct Asymmetric Aldol Reaction in Continuous Flow Using Gel‐Bound Organocatalysts. European Journal of Organic Chemistry, 2021(17), 2578-2586.
  Schmiegel, Carsten J.; Baier, Rene & Kuckling, Dirk
  
• Organic reactions in continues flow using gel-bounded organo-catalysts, conference on Adaptive Polymers and Systems, RWTH Aachen University, Aachen, September 12-14, 2022
  N. Killi
  
• Quinuclidine-Immobilized Porous Polymeric Microparticles as a Compelling Catalyst for the Baylis–Hillman Reaction. ACS Applied Polymer Materials, 4(12), 8996-9005.
  Kumar, Amit; Kuckling, Dirk & Nebhani, Leena
  
• Polymer Networks as Carriers for Organo-catalysts within Continuously Driven Microfluidic Reactor Systems, conference on 14th Advanced Polymers via Macromolecular Engineering” (APME23) in Paris, France, April 23-27, 2023
  N. Killi
  
• Polymeric Networks Containing Amine Derivatives as Organocatalysts for Knoevenagel Reaction within Continuously Driven Microfluidic Reactors. Gels, 9(3), 171.
  Killi, Naresh; Bartenbach, Julian & Kuckling, Dirk
  
• Gel-bounded Organo-catalyst for Baylis-Hillman reaction in Continuously Driven Microfluidic Reactor, Summer School on Catalysis: Understanding and applications, IMT- Mines, Albi, France, June 17-22, 2024
  N. Killi
  
• Synthesis of Curcumin Derivatives via Knoevenagel Reaction Within a Continuously Driven Microfluidic Reactor Using Polymeric Networks Containing Piperidine as a Catalyst. Gels, 11(4), 278.
  Killi, Naresh; Rumpke, Katja & Kuckling, Dirk