DES in polymerisation reactions

The use of deep eutectic solvents (DESs) acting as all-in-one solvent–template–reactant systems offers an interesting green alternative to conventional syntheses in materials science. The use of DESs that contain not only the precursor itself but also some additional components that either provide certain functionality (e.g., drug delivery and controlled release, or electrical conductivity) to the resulting materials or direct their formation with a particular structure (e.g., hierarchical- type) offer an interesting economy of reagents. Moreover, DESs act as a reaction medium, so polymerizations are ultimately carried out in a solventless fashion.

DESs also offer the possibility of using novel precursors – never used in conventional polymerizations – that either favor more efficient polymerization by decreasing the energy input required for reaction progress or allow introducing new funtionalities to the resulting materials.

Representative examples included explored within the last years in our group include:

  1. DES-assisted radical polymerizations of acrylates and methacrylates
  2. DES-assisted formation of polyesters via polycondensation
  3. DES-assisted formation of resorcinol-formaldehyde (using either resorcinol itself or in combination with other phenol derivatives) resins via polycondensation and preparation of 3D hierarchical porous materials

The  resulting DES-based materials have been optimised for their use in a wide variety of applications ranging from energy storage and conversion devices (supercapacitors and metal free electrodes for fuel cells) and environmental science technologies (gas adsorption and separation) to biomedicine.

Please refer to our selected list of publications to have a closer look to our research trajectory.

SELECTED LIST OF PUBLICATIONS
  1. From polymer blends to a block copolymer: Ring-opening polymerization of L-lactide/ε-caprolactone eutectic system                                                         M. Castillo-Santillan, J. R. Torres-Lubian, A. Martínez-Richa, S. T. Huerta-Marcial, M. C. Gutiérrez, K. Loos, M. G. Pérez-García, J. D. Mota-Morales                                  Polymer 2022, 262, 125432.
  2. Carbon-GO composites with preferential water versus ethanol uptake           L. Z. Guan, J. Patiño, C. Cuadrado-Collados, A. Tamayo, M. C. Gutiérrez, M. L. Ferrer, J. Silvestre-Albero, and F. del Monte                                                                       ACS Applied Materials & Interfaces 2019,11 (27), 24493-24503
  3. Predicting the suitability of aqueous solutions of deep eutectic solvents for preparation of co-continuous porous carbons via spinodal decomposition processes 
    E . Posada, N. López-Salas, D. Carriazo, M. A. Muñoz-Márquez, C. O. Ania, R. J. Jiménez-Riobóo, M. C. Gutiérrez, M. L. Ferrer, F. del Monte
    Carbon 2017    , 123, 536-547
  4. Phosphorus-doped carbon-carbon nanotube hierarchical monoliths as true three-dimensional electrodes in supercapacitor cells
    J. Patiño, N. Lopez-Salas, D. Carriazo, M. C. Gutierrez, M. L. Ferrer, F. del Monte
    J. Mater. Chem. A 2016, 4, 1251-1263
  5. Efficient nitrogen-doping and structural control of hierarchical carbons using unconventional precursors in the form of deep eutectic solvents
    N. Lopez-Salas, M. C. Gutierrez, C. Ania, J. L. G. Fierro, M. L. Ferrer, F. del Monte
    J. Mater. Chem. A 2014, 2, 17387-17399
  6. Deep Eutectic Solvents in Polymerizations: A Greener Alternative to Conventional Syntheses
    F del Monte, D. Carriazo, M. C. Serrano, M. C. Gutiérrez, M. Luisa Ferrer ChemSusChem 2014, 7, 999 – 1009
  7. Phosphate-Functionalized Carbon Monoliths from Deep Eutectic Solvents and their Use as Monolithic Electrodes in Supercapacitors
    D. Carriazo, M. C. Gutiérrez, F. Picó, J.M. Rojo, J.L.G. Fierro, M.L. Ferrer, F. Monte ChemSusChem 2012, 5, 1405 – 1409
  8. Synthesis of novel lidocaine-releasing poly(diol-co-citrate) elastomers by using deep eutectic solvents
    M. C. Serrano,   M. C. Gutierrez, R. Jiménez, M. L. Ferrer, F. del Monte
    Chem. Commun. 2012, 48, 579–581
  9. Deep Eutectic Solvents Playing Multiple Roles in the Synthesis of Polymers and Related Materials 
    D. Carriazo, M. C. Serrano, M. C. Gutierrez, M. L. Ferrer, F. del Monte
    Chem. Soc. Rev. 2012, 41, 4996 – 5014
  10. Deep Eutectic Assisted Synthesis of Carbon Adsorbents Highly Suitable for  Low-Pressure Separation of CO2/CH4 Gas Mixtures 
    J. Patiño, M. C. Gutierrez, D. Carriazo, C. Ania, J. Parra, M. L. Ferrer, F. del Monte
    Energy Environ. Sci. 2012    , 5, 8699-8707
  11. Deep Eutectic Solvents as Both Precursors and Structure Directing Agents in the Synthesis of Nitrogen Doped Hierarchical Carbons Highly Suitable for CO2 Capture
    M. C. Gutierrez, D. Carriazo, C. Ania, J. Parra, M. L. Ferrer, F. del Monte
    Energy Environ. Sci. 2011, 4, 3535-3544
  12. Frontal polymerizations carried out in deep-eutectic mixtures providing both the monomers and the polymerization medium
    J. D. Mora-Morales, M. C. Gutierrez, I. C. Sanchez, G. Luna-Barcenas, F. del Monte
    Chem. Commun. 2011, 47, 5328–5330
  13. Resorcinol-Based Deep Eutectic Solvents as Both Carbonaceous Precursors and Templating Agents in the Synthesis of Hierarchical Porous Carbon Monoliths 
    D. Carriazo, M. C. Gutierrez, M. L. Ferrer, F. del Monte
    Chem. Mater.     2010, 22, 6146