Continuous Controlled Radical Polymerization of Methyl Acrylate in a Copper Tubular Reactor

Abstract

The use of copper tubing as both the reactor and as a catalyst source is demonstrated for continuous controlled radical polymerization of methyl acrylate at ambient temperature and at low solvent content of 30%. The high surface area provided by the copper walls mediates the reaction via the single electron transfer-living radical polymerization (SET-LRP) mechanism. The polymerizations proceeded quickly, reaching 67% conversion at a residence time of 16 min. Ligand concentration could also be reduced without a sharp drop in polymerization rate, demonstrating the potential for decreased raw material and post-process purification costs. Chain extension experiments conducted using synthesized polymer showed high livingness. The combination of living polymer produced at high polymerization rates at ambient temperature and low volatile organic solvent content demonstrate the potential of a copper reactor for scale up of SET-LRP.

Copper‐mediated controlled radical polymerization in continuous flow processes: Synergy between polymer reaction engineering and innovative chemistry

“…To demonstrate this concept, we first investigated the use of copper tubing to construct a continuous flow tubular reactor wherein the walls of the reactor acted as a catalyst source . Although the literature studies have used copper powder and copper wire as a catalyst source, immobilization of these two forms of copper could prove challenging and other issues such as clogging of the reactor with low‐solvent‐content recipes were anticipated.…”

SET‐LRP of acrylonitrile catalyzed by tin powder

“…This means that SET‐LRP provides access to a broader range of initiators, monomers, catalysts, and synthesis for the synthesis of macromolecules with complex architecture 33–35. For example, SET‐LRP is remarkably effective for a wide variety of important monomers such as functional acrylates,4,22,36 acrylamides,37,38 methacrylates,25,27,39–45 methacrylic acid,46,47 vinyl chloride,4,6,22,48,49 and acrylonitrile (AN) 50…”

A Continuous Flow Process for the Radical Induced End Group Removal of RAFT Polymers

“…With the emergence of microreactor technology in recent years,20–24 polymerizations have been performed in continuous flow processing on laboratory scale 25–32. The continuous method can offer a range of benefits over batch processing, which is the classical choice in a lab environment; flow reactors have, e.g., better heat and mass transfer properties, leading to increased control over the process and often to improvements in polymer product quality.…”

“…The process produced narrow molecular weight distribution polymers with polydispersity, Ð , typically below 1.20. While continuous flow synthesis of polymers has been reported in a multitude of publications,25–32 post‐processing of polymer solutions via chemical transformations has drawn very little attention up to the present date.…”