NMR as a probe of nanostructured domains in ionic liquids: Does domain segregation explain increased performance of free radical polymerisation?

Puttick, Simon; Davis, Adrienne L.; Butler, Kevin; Lambert, Lynette K.; harfi, Jaouad El; Irvine, Derek J.; Whittaker, Andrew K.; Thurecht, Kristofer J.; Licence, Peter

doi:10.1039/c1sc00207d

Cited by 28 publications

(26 citation statements)

References 43 publications

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“…They speculate that this behavior is due to locally ordered structures in the RTILs, which favor propagation (similar to subsequent findings reported in Ref. 43. This group also studied copolymerization on nonpolar and zwitterionic methacrylates in RTILs (48) as well as the use of 1-alkyl-3-methylimidazolium tosylates as solvents for polymerization of n-butylmethacylate and styrene, where high yields and high molecular weights were obtained (49).…”

Section: Free Radical Polymerizationsupporting

confidence: 54%

Polymerization in Ionic Liquids

Zhang

Behera

Hong

et al. 2015

Encyclopedia of Polymer Science and Technology

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Room temperature ionic liquids (RTILs) have proved over recent years to be useful and unique reaction media for a variety of chemical reactions. Faster reaction rates and better selectivities are often observed in RTILs as compared to those in common organic solvents. In addition to these advantages, the low volatility, nonflammability, and recycling potential also help RTILs become a preferred alternative reaction medium to meet environmental and other requirements. This is evidenced by the ever increasing number of papers published in this area every year and interesting and important discoveries. When conventional free radical polymerizations are carried out in RTILs, there is an increase in the propagation rate due to the high polarity of the RTIL and a decrease in the termination rate because of the high viscosity of the RTILs, and thus the overall reaction rate is greatly increased along with an increase in molecular weight. For living/controlled polymerization such as atom transfer radical polymerization and radical addition‐fragmentation and transfer, the reactions in RTILs are still controllable with faster reaction rates and easy separation of catalysts and/or ligands from the resulting polymers. Nearly all types of polymerization processes have now been successfully conducted in RTILs, often with advantageous effects.

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Section: Free Radical Polymerizationsupporting

confidence: 54%

Polymerization in Ionic Liquids

Zhang

Behera

Hong

et al. 2015

Encyclopedia of Polymer Science and Technology

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“…40,41 Exploration of the causes underlying the increased polymerization rates in IL solvents suggests that the improvements are due, at least in part, to the localization of the dissolved monomers into the polar or nonpolar domains within the IL media. 42,43 Certain…”

Section: 24-6mentioning

confidence: 98%

Photopolymerization of coordinated ionic liquid monomers: Realizing the benefits of structured media using only common reagents

Whitley

Adams

Terrill

et al. 2016

J. Polym. Sci. Part A: Polym. Chem.

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Here, we provide a detailed report on a new type of structured media for improving photopolymerizations: coordinated ionic liquids (ILs). Coordinated ILs are readily formed from the bistriflimide ([Tf 2 N] 2 ) anion and coordination complexes composed of Li 1 cations with polar organic monomers without an additional cosolvent. Photopolymerization kinetics and monomer conversion were monitored in real time using attenuated total reflectance Fourier transform infrared spectroscopy and the material properties of the products were examined using gel permeation chromatography and differential scanning calorimetry. Generally, coordinated IL monomers displayed improved reaction kinetics at both high and low salt concentrations as well as distinct product properties. The noncovalent (and reversible) interactions between monomer and salt in coordinated ILs hold promise as an efficient and versatile form of structured media for photopolymerizations.

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“…This approach has been successfully applied several times in the study of the imidazolium series of ILs. [23][24][25][26][27] The separation of the intra-and intermolecular dipolar contacts can be done a posteriori by applying the distance threshold of 4 Å for vanishing ROEs. The average distances between the H atoms of interest in cations 1 and 3 were calculated at DFT level (see the SI) and used to assign intra-and intermolecular ROEs, e.g.…”

Section: Internuclear Contacts Via Nuclear Overhauser Enhancementsmentioning

confidence: 99%

Pyrazolium- versus Imidazolium-Based Ionic Liquids: Structure, Dynamics and Physicochemical Properties

et al. 2013

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NMR as a probe of nanostructured domains in ionic liquids: Does domain segregation explain increased performance of free radical polymerisation?

Cited by 28 publications

References 43 publications

Polymerization in Ionic Liquids

Polymerization in Ionic Liquids

Photopolymerization of coordinated ionic liquid monomers: Realizing the benefits of structured media using only common reagents

Pyrazolium- versus Imidazolium-Based Ionic Liquids: Structure, Dynamics and Physicochemical Properties

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