Scalable and Self-Degassing Process for Atom Transfer Radical Polymerization Controlled by Electrochemistry

KEYWORDS: ATRP; Controlled Radical Polymerizations; Oxygen Tolerance; Polymers; Scale-up.

Existing methods for large scale controlled radical polymerization still do not include deoxygenation of the polymerization mixture. Since degassing of a (very) large mixture is not feasible at (very) large scale, dissolved oxygen has to be (electro)chemically washed out of the mixture. Our technology enables the production of various (co)polymers on a large scale by integrating an electrochemical cycle for oxygen scavenging into the polymerization equilibrium:

1. The reaction is then easier to prepare, handle and trigger in the presence of the low-cost sodium pyruvate scrubber. The control over the macromolecular properties is very tight;

2. Our reactors do not require expensive electrodes, are scalable beyond 15 L, and are powered by renewable energy. At 15 L, the maximum power is 1 watt.

Unlike existing methods, there is no need for high-vacuum degassing, purging, or extensive surface cleaning prior to electrolysis. The reactor cleans its own surface and the oxygen is converted into harmless by-products by the same catalyst used in the polymerization. This process is compatible with a wide range of hydrophilic monomers, and can be used for scalable production of high-specialty polymers.

The 18 L full scale reactor loaded with 15 L of polymerization mixture | Kinetics of eATRP of acrylamide from 0.04 to 15 L


Electrochemical self-degassing of the polymerization mixture with inexpensive ROS scavengers.

Electrochemical self-cleaning of surface reactor before the electrolysis.

Tight control of molecular weight and dispersity up to 15 L and beyond.

Near room temperature process.

Compatible with water and aqueous mixtures.

Minimal energy requirements (only 1 W of peak power at 15 L).

No expensive electrodes are needed.

Further scalability beyond 15 L.

Operates as batch reactor, with semibatch possibilities.


Large volume synthesis of controlled linear homopolymers for different application (e.g thickening agents, flocculants, thermoresponsive (co)polymers…).

Large volume synthesis of controlled star-shaped (co)polymers (e. g rheology modifiers).

Large volume synthesis of controlled cationic (co)polymers (e.g antimibrobial polymers).

Large volume synthesis of controlled statistical (co)polymers (e.g lubricants additives).

Large volume synthesis of controlled biocompatible (co)polymers.

Large volume synthesis of engineered cellulose-(co)polymer materials.


IPR LEGAL STATUS: Patent Panding n.º 117852 filed on 11/03/2022.

OWNERSHIP: The rights to the technology are held by the University of Coimbra.

COLLABORATION SOUGHT: The University of Coimbra is seeking commercial partners interested in further developing the technology under a collaboration and license agreement or acquiring the existing rights.


Luís Silva

Innovation Manager

Laura Alho

IP Manager
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