Synthesis and characterization of potentially polymerizable amine-derived ionic liquids bearing 4-vinylbenzyl group

Article abstract of DOI:10.1016/j.molliq.2019.03.061

The syntheses and full spectral (NMR, MS, IR), thermal (DSC) and ion chromatographic characterization of two series of amine-derived ionic liquids bearing 4-vinylbenzyl substituent and having chloride or bis(trifluoromethanesulfonyl)amide anion have been

Full text of DOI:10.1016/j.molliq.2019.03.061

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Synthesis and characterization of potentially polymerizable
amine-derived ionic liquids bearing 4-vinylbenzyl group
Adrian Zajac, Andrea Szpecht, Dawid Zielinski, Krzysztof Rola,
Jakub Hoppe, Katarzyna Komorowska, Marcin Smiglak
PII:
S0167-7322(18)36361-X
DOI:
Reference:
https://doi.org/10.1016/j.molliq.2019.03.061
MOLLIQ 10602
To appear in:
Journal of Molecular Liquids
Received date:
Revised date:
Accepted date:
6 December 2018
30 January 2019
12 March 2019
Please cite this article as: A. Zajac, A. Szpecht, D. Zielinski, et al., Synthesis and
characterization of potentially polymerizable amine-derived ionic liquids bearing
4-vinylbenzyl group, Journal of Molecular Liquids, https://doi.org/10.1016/
j.molliq.2019.03.061
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Synthesis and characterization of potentially polymerizable amine-derived
ionic liquids bearing 4-vinylbenzyl group
Adrian Zajac,1* Andrea Szpecht,1,2 Dawid Zielinski,1 Krzysztof Rola,3 Jakub Hoppe,1,2 Katarzyna
Komorowska,3,4 Marcin Smiglak1*
1
Materials Synthesis Group, Poznan Science and Technology Park, Adam Mickiewicz University
Foundation, ul. Rubiez 46, 61-612 Poznan
2 Faculty of Chemistry, Adam Mickiewicz University, ul. Umultowska 89 B, 61-614 Poznan, Poland
3 PORT sp. z o.o., ul. Stablowicka 147, 54-066 Wroclaw
4
Department of Optics and Photonics, Faculty of Fundamental Problems of Technology, ul. Wyb.
Wyspianskiego 27, 50-370 Wroclaw University of Science and Technology, Wroclaw, Poland
Corresponding authors: adrian.zajac@ppnt.poznan.pl; marcin.smiglak@gmail.com

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Abstract: The syntheses and full spectral (NMR, MS, IR), thermal (DSC) and ion chromatographic
characterization of two series of amine-derived ionic liquids bearing 4-vinylbenzyl substituent and
having chloride or bis(trifluoromethanesulfonyl)amide anion have been presented. The analysis of the
dependence between 1H NMR chemical shift value of selected protons and the structure of cation and
anion has been undertaken. Not described before in the literature results of ion chromatographic
analysis of obtained compounds have been discussed. The polymerization potential of selected
isolated compounds has been briefly described on the base of DSC measurements and electron beam
polymerization experiments. Mentioned experiments revealed that presented ionic liquids are prone to
polymerization both in solution and pure form under temperature (DSC) or electron beam irradiation
to form solid polymeric products, at micrometer scale in the latter case.
Keywords: ionic liquids, polymerizable ionic liquids, NMR, ion chromatography, DSC, electron beam
polymerization, photonics
Introduction
The research on ionic liquids has been continuing for many decades,1 nevertheless they still attract
unabated interest of the scientific community. It is due to their very interesting properties such as e.g.
combination of hydrophilic and hydrophobic features, liquid state below 100 °C together with ionic
structure, extremely low volatility, high chemical inertness, thermal stability and wide range of a
structural diversity. Their properties can be additionally adjusted by mixing with molecular liquids,
such as water or organic solvents.2 All of this characteristics predestine these compounds to play
significant role in many fields,3 i.a. as green solvents in small molecules reactions,4 solvents for
biopolymers,5,6 polymerizations,7,8 catalyses,9,10 biocatalyses,11 and enzymatic resolutions,12 as
convenient extraction solvents for organic compounds13,14,15 and metals,16,17,18 as liquid membranes,19
mobile and stationary phase additives in liquid chromatography,20,21,22 catalysts,23,24 electrochemical
sensors,25,26,27,28 conducting factors in energy storage and conversion materials and devices (batteries,
solar cells, supercapacitors),29,30,31,32,33 energetic materials,34,35,36,37 lubricants,38 silk dyeing accelerating

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agents,39 bacteri- and fungicidals,40 plant systemic acquired resistance inducers,41,42, drug delivery
tools,43 solvents for polymorphic drugs transformations44,45 and pharmaceuticals,46,47 just to name few.
Another significant advantage of ILs is a simplicity of their synthesis. Numerous known synthetic
procedures are highly efficient and facile, resistant to ambient factors such as humidity or oxygen and
characterized by high level of atom economy (often reaching 100%).48,49 Substrates used are usually
inexpensive and commercially available.
Potentially polymerizable ionic liquids bearing unsaturated substituent(s) seem to attract increasing
attention in particular. They can combine all of the characteristics of an ionic liquid state and
potentially available corresponding polymer. Many polymers of that kind are known and utilized, most
of all, as conductive polymers50,51,52,53,54,55 but also in large variety of applications, e.g., surfactants,56
sorbents,57,58 electrocatalysts,59 membranes,60,61 GC stationary phases,62 molecularly imprinted
polymers,63 light-emitting cells,64 UV-imprint resists65 and dental compositions.66
It is well-known from the literature that the common feature of polymerizable ionic liquids is the
presence of terminal double bond in one or more substituents of ionic core, cationic in most
cases.67,68,69 The presence of terminal double bond is significantly convenient in those compounds due
to the relative simplicity of its introduction to the ionic liquid structure and its predisposition to radical
polymerization processes.
Polymerized ionic liquids or ionic polymers can be obtain in three main ways: (i) radical
polymerization of ionic liquid monomers, (ii) post-polymerization processing of neutral polymers and
(iii) copolymerization by cross-linking of existing polymeric ionic liquid chain with another one.69
Two latter methods are not the subject of this article, therefore we focus on the radical polymerization.
In general, the method is implemented by the addition of a proper initiator (e.g. AIBN) and the use of
heating or UV irradiation of the reaction mixture.69 Polymeric ionic liquids can also be successfully
synthesized by: (i) reversible addition fragmentation transfer polymerization and (ii) radical
polymerization mediated by atom transfer, cobalt, copper, nitroxide, methyl methacrylate,
organometallics etc.69
Herein we would like to present syntheses and full characterization of series of unsaturated amine-
derived ionic liquids bearing 4-vinylbenzyl moiety. We chose this group of compounds due to the