The use of untreated water as polymerization solvent could reduce costs of ATRP at industrial scale


Several polymerization methods for the synthesis of polymeric materials are available. Among them, atom transfer radical polymerization (ATRP) techniques have been effectively used to synthesize both homopolymers and block copolymers with well-defined structure, composition and molecular weight. Considering the increasing call for environmental protection, the use of eco-friendly solvents during polymer preparation is highly encouraged thus attracting significant attention of researchers.

Previously, solvents were shown to have general impact on the environment, health, safety and overall cost of polymer production. As such, the use of efficient solvents with eco-friendly character is highly desirable. Alternatively, water which is highly used as a solvent in most of the industrial processes has been identified as a promising solution. Unfortunately, the impurities contained in water may lead to adverse effects on ATRP reactions. To this note, the use of untreated water as solvent has been identified as a promising candidate for enhancing the efficiency of the industrial ATRP processes.

A group of researchers at the University of Coimbra: Dr. Patricia Mendonça, Andreia Oliveira (MSc), Jessica Ribeiro (Msc), Professor Ana Castilho, Professor Arménio Serra, and Professor Jorge Coelho assessed the feasibility of untreated water as a polymerization solvent. Fundamentally, they used different ATRP variation techniques for the synthesis of several water-soluble polymers. Their research work was published in the research journal, Polymer Chemistry.

In brief, the research team first harnessed untreated water with varying ionic composition from different natural sources i.e. rainwater, rivers and springs. Next, without purification, the untreated water was used as the polymerization solvent for the synthesis of four different water-soluble polymers by several ATRP variations. The polymers included: poly(2-hydroxyethyl acrylate) (PHEA), poly(ethylene glycol)-b-poly(2-aminoethyl methacrylate hydrochloride) (PEG-b-PAMA) block copolymer, poly[oligo(ethylene oxide) methyl ether acrylate] (POEOA), and poly((3-acrylamidopropyl)trimethylammonium chloride) PAMPTMA.

The authors confirmed the feasibility of using untreated water as the polymerization solvent for the synthesis of various polymeric materials with sufficient control over the molecular weight. For instance, the polymerization kinetic were observed to be similar to those obtained using ultrapure deionized water as solvent. Furthermore, it was worth noting that high concentration of halide salts such as sodium chloride (sea water) could be used in the polymerization of neutral OEOA monomer without any major effects on the control over molecular weight or polymerization kinetics.

In summary, Patrícia Mendonça and colleagues successfully presented the significance of using untreated water as polymerization solvent for the synthesis of water-soluble polymers by ATRP. Altogether, the study provides vital information that will pave way for the development of low-cost ATRP processes for large scale industrial applications.

The use of untreated water as polymerization solvent could reduce costs of ATRP at industrial scale - Advances in Engineering

About the author

Ana Maria Castilho is an Assistant Professor at the Department of Earth Sciences at the University of Coimbra (Portugal), where she has been teaching since 1994. She has a degree in geological engineering and completed her PhD in hydrogeology and water resources, at the University of Coimbra, in 2009. Her research focuses on hydrogeology, surface and groundwater interactions, hydrochemistry and environmental engineering. She published 8 peer-reviewed papers and 5 book chapters in the areas of Earth Sciences and Environment and Engineering and Technology and is a member of IAH, IWA and CGeo, a R&D multidisciplinary unit in the earth sciences domain.

About the author

Andreia Oliveira completed her M.S. degree in Chemistry at the University of Coimbra (Portugal) in 2014. From 2016 to 2017, she worked as a research fellow at the Organic Chemistry Group at the University of Coimbra, where she gained experience in the field of organic chemistry and medicinal chemistry. Since 2018, she has been a research fellow at the research group PolySyc from the Chemical Engineering Department at the University of Coimbra.

Her current research is focused on antimicrobial polymers and on the design of well-defined macromolecules by atom transfer radical polymerization.

About the author

Arménio C. Serra (born in 1964) studied biochemistry at the University of Coimbra (Portugal) and completed his doctorate in Organic Chemistry in 1998. His academic work started with the study of sulfonyl radical reactions, followed by the synthesis of porphyrin macrocycles to be used as photooxidation catalysts and in photodynamic therapy. Other areas of work included the synthesis of supported organic catalysts for carbon-carbon condensation reactions and carbon dioxide activation. Presently, he is professor at the Chemical Engineering Department of the University of Coimbra.

His research topics are centered on the study of controlled polymerization processes and the transformation of biomolecules in order to be used in material and health sciences.

About the author

Jessica Ribeiro completed her M.S. degree in Medicinal Chemistry at the University of Beira Interior (Portugal) in 2016. In 2017 she embraced the opportunity to work as a research fellow at PolySyc research group at the University of Coimbra (Portugal).

Her work has been focused on the development of new eco-friendly atom transfer radical polymerization methods and on the controlled polymerization of new bio-based monomers, to obtain polymers with improved properties, through different reversible deactivation radical polymerization techniques.

About the author

Jorge F. J. Coelho was born in Figueira da Foz, Portugal, in 1978. He graduated from the Faculty of Science and Technology of the University of Coimbra, Portugal, in Chemical Engineering. In 2006, he obtained his PhD from the University of Coimbra working on new reversible deactivation radical polymerization methods for vinyl chloride. At the moment, he is Full Professor at the University of Coimbra.

He has co-authored 147 peer-reviewed research papers, 12 book chapters and 3 granted international patents. His research interests include reversible deactivation radical polymerization, bio-based and biodegradable polymers, novel pharmaceutical products, supramolecular chemistry and scale-up approaches for reversible deactivation radical polymerization

About the author

Patrícia Mendonça has studied chemical engineering and completed her PhD at University of Coimbra (Portugal) in 2015. During both PhD and postdoctoral research projects, she has conducted part of the work at Carnegie Mellon University under the supervision of Professor Krzysztof Matyjaszewski. In 2019 she became a junior research associate at the University of Coimbra, leading part of the team of the PolySyc research group at the Chemical Engineering Department.

Her research interests include reversible deactivation radical polymerization techniques, mainly atom transfer radical polymerization, antimicrobial polymers, design of well-defined polymers and eco-friendly polymerization systems.


Mendonça, P., Oliveira, A.S.R., Ribeiro, J.P.M., Castilho, A., Serra, A.C., & Coelho, J.F.J. (2019). Pushing the limits of robust and eco-friendly ATRP processes: untreated water as the solvent. Polymer Chemistry, 10(8), 938-944.

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