Kinetic Studies of Photopolymerization of Monomer‐Containing Deep Eutectic Solvents

Fazende, Kylee F.; Gary, Daniel P.; Mota‐Morales, Josué D.

doi:10.1002/macp.201900511

Cited by 25 publications

(20 citation statements)

References 47 publications

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“…This process is more pronounced for choline-based compositions. Furthermore, the higher viscosity of deep eutectic solvents has been proposed as one of the factors leading to an enhancement of the radical polymerisation rate [ 86 ], and this can be the reason for the higher degree of grafting of the AA/ChCl solvent in our case. Additionally, the lower accessibility of the cellulose surface for acrylic acid in the case of the 1-butyl-3-methylimidazolium chloride-based solvent can be speculated, but this needs further evaluation and is beyond the scope of the current study.…”

Section: Discussionmentioning

confidence: 88%

Polymerizable Choline- and Imidazolium-Based Ionic Liquids Reinforced with Bacterial Cellulose for 3D-Printing

et al. 2021

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In this work, a novel approach is demonstrated for 3D-printing of bacterial cellulose (BC) reinforced UV-curable ion gels using two-component solvents based on 1-butyl-3-methylimidazolium chloride or choline chloride combined with acrylic acid. Preservation of cellulose’s crystalline and nanofibrous structure is demonstrated using wide-angle X-ray diffraction (WAXD) and atomic force microscopy (AFM). Rheological measurements reveal that cholinium-based systems, in comparison with imidazolium-based ones, are characterised with lower viscosity at low shear rates and improved stability against phase separation at high shear rates. Grafting of poly(acrylic acid) onto the surfaces of cellulose nanofibers during UV-induced polymerization of acrylic acid results in higher elongation at break for choline chloride-based compositions: 175% in comparison with 94% for imidazolium-based systems as well as enhanced mechanical properties in compression mode. As a result, cholinium-based BC ion gels containing acrylic acid can be considered as more suitable for 3D-printing of objects with improved mechanical properties due to increased dispersion stability and filler/matrix interaction.

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Section: Discussionmentioning

confidence: 88%

Polymerizable Choline- and Imidazolium-Based Ionic Liquids Reinforced with Bacterial Cellulose for 3D-Printing

et al. 2021

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“…42−44 Some reports on free-radical polymerization in DESs also suggested an enhanced polymerization rate. 44,46 On the other hand, ionic liquids have been intensively explored for free-radical polymerization, 32 including several reports on RAFT polymerization. 60−62 Interestingly, the polymerization rate in ionic liquids was also faster than that in bulk or in common organic solvents.…”

Section: Discussionmentioning

confidence: 99%

“…As mentioned earlier, RDRP in DESs has only been studied sporadically. − Some reports on free-radical polymerization in DESs also suggested an enhanced polymerization rate. , On the other hand, ionic liquids have been intensively explored for free-radical polymerization, including several reports on RAFT polymerization. − Interestingly, the polymerization rate in ionic liquids was also faster than that in bulk or in common organic solvents. The major hypothesis for the enhanced rate in ionic liquid was attributed to the protected radical effect by the formation of small monomer domains within the ionic liquids .…”

Section: Discussionmentioning

confidence: 99%

“…DESs have also been considered as candidates for a wide range of polymer synthesis and processing . Some recent works have attempted to use DESs for RDRP. − Interestingly, the polymerization rate in DESs could be faster than that in bulk or in common organic solvents, ,, although the extent of rate enhancement and the underlying mechanism have not been systematically investigated. Inspired by the abovementioned works, we hypothesize that DESs may provide an effective strategy to increase the polymerization rate of photo-induced RAFT polymerization and reduce its environmental impacts.…”

Section: Introductionmentioning

confidence: 99%

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Efficient Visible-Light-Driven RAFT Polymerization Mediated by Deep Eutectic Solvents under an Open-to-Air Environment

2021

Macromolecules

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In this work, we investigate the effects of deep eutectic solvents (DESs) on a facile reversible addition− fragmentation chain-transfer (RAFT) polymerization driven by visible light. A DES composed of tetrabutylammonium chloride (TBACl) and ethylene glycol served as a nonvolatile medium for a variety of monomers, including methyl methacrylate, methyl acrylate, dimethylacrylamide, and styrene. We first employed the polymerization-through pathway to overcome oxygen inhibition in an open-to-air environment using methyl methacrylate as the model compound. The photoiniferter polymerization using trithiocarbonates as the chain transfer agent (CTA) in DESs exhibited enhanced polymerization rates and achieved a narrow molecular weight distribution. Interestingly, even dithiobenzoate, the CTA with low efficiency for photoiniferter polymerization, exhibited a nearly 4.5-fold increase in the apparent polymerization rate constants when compared to the reaction in dimethyl sulfoxide. Moreover, the stability of the CTAs was increased in DESs for efficient control of molecular weight distribution and preservation of functional chain ends. We then surveyed photocatalysts for photoelectron/energy transfer (PET) RAFT polymerization and found that eosin Y was compatible with DESs. The PET-RAFT polymerization using dithiobenzoate in DESs showed even higher polymerization rates than the photoiniferter polymerization and enabled the polymerization under natural sunlight. Besides methyl methacrylate, other monomers also exhibited an increased polymerization rate in DESs, comparable to reactions in ionic liquids. These results suggest that DESs are effective and green media to facilitate photo-induced RAFT polymerization without additives or tedious degassing processes.

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“…2A and Fig Photoinitiators have also been employed to facilitate the free-radical polymerization of monomers in DES systems, in addition to polymerizable eutectics, under particularly mild reaction conditions. Fazende et al [65] highlighted the impact of polymerizable eutectics with respect to accelerated reaction kinetics via photopolymerization. Using the common photoinitiator diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide (TPO) at a loading of 0.1 mol%, acrylic acid (AA) and methacrylic acid (MAA) showed no polymerization within 90 min via visible light irradiation.…”

Section: Free-radical Polymerizationmentioning

confidence: 99%

Greener, Faster, Stronger: The Benefits of Deep Eutectic Solvents in Polymer and Materials Science

2021

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Deep eutectic solvents (DESs) represent an emergent class of green designer solvents that find numerous applications in different aspects of chemical synthesis. A particularly appealing aspect of DES systems is their simplicity of preparation, combined with inexpensive, readily available starting materials to yield solvents with appealing properties (negligible volatility, non-flammability and high solvation capacity). In the context of polymer science, DES systems not only offer an appealing route towards replacing hazardous volatile organic solvents (VOCs), but can serve multiple roles including those of solvent, monomer and templating agent—so called “polymerizable eutectics.” In this review, we look at DES systems and polymerizable eutectics and their application in polymer materials synthesis, including various mechanisms of polymer formation, hydrogel design, porous monoliths, and molecularly imprinted polymers. We provide a comparative study of these systems alongside traditional synthetic approaches, highlighting not only the benefit of replacing VOCs from the perspective of environmental sustainability, but also the materials advantage with respect to mechanical and thermal properties of the polymers formed.

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Kinetic Studies of Photopolymerization of Monomer‐Containing Deep Eutectic Solvents

Cited by 25 publications

References 47 publications

Polymerizable Choline- and Imidazolium-Based Ionic Liquids Reinforced with Bacterial Cellulose for 3D-Printing

Polymerizable Choline- and Imidazolium-Based Ionic Liquids Reinforced with Bacterial Cellulose for 3D-Printing

Efficient Visible-Light-Driven RAFT Polymerization Mediated by Deep Eutectic Solvents under an Open-to-Air Environment

Greener, Faster, Stronger: The Benefits of Deep Eutectic Solvents in Polymer and Materials Science

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