Polymerization of Monomeric Ionic Liquid Confined within Uniaxial

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Polymerization of Monomeric Ionic Liquid Confined within Uniaxial Alumina Pores as a New Way of Obtaining Materials with Enhanced Conductivity Magdalena Tarnacka, Anna Chrobok, Karolina Matuszek, Sylwia Golba, Paulina Maksym, Kamil Kaminski, and Marian Paluch ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b10666 • Publication Date (Web): 06 Oct 2016 Downloaded from http://pubs.acs.org on October 7, 2016

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ACS Applied Materials & Interfaces

Polymerization of Monomeric Ionic Liquid Confined within Uniaxial Alumina Pores as a New Way of Obtaining Materials with Enhanced Conductivity Magdalena Tarnacka†‡*, Anna Chrobok#, Karolina Matuszek#, Sylwia Golba§, Paulina Maksym$, Kamil Kaminski†‡*, Marian Paluch†‡

* Corresponding authors: (MT) [email protected], (KK) [email protected]

† Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007 Katowice, Poland ‡ Silesian Center for Education and Interdisciplinary Research, University of Silesia, 75 Pulku Piechoty 1A, 41-500 Chorzow, Poland # Department of Chemical Organic Technology and Petrochemistry, Silesian University of Technology, Krzywoustego 4, 44-100 Gliwice, Poland § Institute of Materials Science, University of Silesia, 75 Pulk Piechoty 1A, 41-500 Chorzow, Poland $ Department of Physical Chemistry and Technology of Polymers, Faculty of Chemistry, Silesian University of Technology, Strzody 9, 44-100 Gliwice, Poland

Abstract Broadband Dielectric Spectroscopy (BDS) and Differential Scanning Calorimetry (DSC) have been employed to probe dynamics and charge transport of 1-butyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide ([bvim][NTf2]) confined in native uniaxial AAO pores as

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well as to study kinetics of radical polymerization of the examined compound as a function of the degree of confinement. Subsequently, the electronic conductivity of the produced polymers was investigated. As observed, polymerization carried out at T = 363 K proceeds faster under confinement with some saturation effect observed for the sample in pores of smaller diameter. Obtained results were discussed in the context of the very recent reports showing that free volume of the confined material is higher with respect to the bulk one. It was also noted that conductivity of poly[bvim][NTf2] is significantly higher with respect to the macromolecules obtained upon bulk polymerization. Moreover, charge transport of the confined macromolecules is even higher when compared to the bulk monomeric ionic liquid at some thermodynamic conditions. Additionally, the molecular weight, Mw, of the confinedsynthesized polymers is significantly higher with respect to the bulk-synthesized material. Interestingly, both parameters: (i) the enhancement of σdc and (ii) the increased Mw can be tuned and controlled by the application of the appropriate confinement. Consequently, those results are quite promising in the context of development of the fabrication of polymerized ionic liquids (PILs) nanomaterials of unique properties and morphologies, which can be further easily applied in the field of nanotechnology.

KEYWORDS: Monomeric Ionic Liquid, Molecular Dynamics, Polymerization Kinetics, Dielectric Spectroscopy, Charge Transport.

1. INTRODUCTION Ionic liquids (ILs) are an important class of chemical compounds, which due to unique properties, like good chemical and electrochemical stability, non-flammability, negligible vapor pressure and high ionic conductivity, attract an increasing attention. Although widely promoted as “green solvents” for, i.e. organic synthesis, polymerization or extraction


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processes1,2, they are currently investigated as potential electrolytes for application in electronic industry, mainly in case of lithium ion batteries3, solar batteries4 and fuel cells5,6. However due to the issue of i.e. leakage or non-portability, their role in electronic devices remains a complex mater. A solution might be the polymer-based materials, including gels, rubber or nanocomposites, combining the unique properties of ILs with the macromolecular architecture of polymers, which allows the production of conductive materials of various sizes, shapes and geometries7,8. Hence, the polymer-based electrolytes can be successfully applied as, i.e. (i) thin films, providing a good electrode–electrolyte contact, or (ii) a replacement of conventional media as organic solvents in lithium batteries (i.e. liquid electrolytes based on lithium salt dissolved in low molecular weight organic carbonates) and water in fuel cells, improving their safety as well as thermal and electrochemical stabilities at high temperatures. The polymer-based electrolytes materials can be produced by three ways: (i) doping of polymers with ILs, (ii) polymerization (or crosslinking) of monomers in ILs and (iii) synthesis of polymerized ionic liquids (PILs)8. While the former two approaches allow to obtain materials from conventional compounds; the later one leads to the production of functional polymers with the features of ILs. Further, the polymerization of monomeric ionic liquids (MILs) within the spatially restricted spaces might allow to obtain unique polymer morphologies and to control properties on the nanometric length scale9,10,11,12, similar as in case of conventional (non-conductive) materials13,14,15,16,17,18,19,20. One can recall that nanoconfinement conditions enforce the defined geometry of the nascent polymers, according to the properties of applied nanoreactores. Thus, the production of nanotubules or nanowires with potential applications as i.e. biosensors or electrical and electrooptical devices can be achieved9,21. Although, the comprehensive study on the PILs nanosystems is still lacking, this class of materials already reveals a potential versatility of application



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especially in context of some surprising and promising features noticed in case of both conductive and non-conductive nanomaterials. Interestingly for radical polymerization performed under confinement conditions in case of i.e. styrene and methyl methacrylate, it was clearly noted that the macromolecules obtained under spatial restriction can be characterized by lower dispersity (PDI) than their bulk counterparts14,15,22. Moreover, this effect was observed to be confinement dependent and increases with the reduction of the host channel size. The reduction of dispersity was discussed in the context of unique properties of the matrix (porous coordination polymers, PCP), which stabilized the propagating radicals by efficient suppression of termination step of the reaction, realizing living radical polymerization scenario with better control over the reaction14,23,24. Furthermore, it was also observed that the application of nanocavities increases the molecular weight of poly(methyl methacrylate) (PMMA) in comparison to the bulk-synthesized polymers25,26,27. In this context, it is worthwhile to mention recent paper by Giussi et al.15 on the radical polymerization of styrene carried out within the anodic aluminium oxide (AAO) templates. The authors reported that, at early stage of the reaction, bulk and nanosystem can be characterized by similar values of Mw and PDI. However above the certain degree of conversion (65 %), both variables increase much more significantly in case of bulk-synthesized polymer15. On the other hand, the detailed analysis of the recovered polymers revealed that the reduced space of nanoreactors has a significant influence also on the stereoregularity of obtained macromolecules. It was observed that the tacticity of polymers formed under confinement condition is a function of the pore diameter of given host materials. As reported in case of vinyl polymers: poly(vinyl acetate), polystyrene and PMMA, the ratio of isotactic units increases with a growth in spatial restriction due to increasing host-guest interactions14. However, numerous works have shown that the mutual interactions between the monomer and the matrix can be easily changed by either the


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chemical or shape modification of the host yielding to the enlarged control of the properties of produced polymers. Here, we examined the charge transport and molecular dynamics of the monomeric ionic

liquid

(MIL)

1-butyl-3-vinylimidazolium

bis(trifluoromethanesulfonyl)imide

([bvim][NTf2]) and its polymer counterpart (poly[bvim][NTf2]) obtained by radical polymerization of the monomer confined within nanoporous aluminum oxide (AAO) membranes of various pore diameter by means of Broadband Dielectric Spectroscopy (BDS) and Differential Scanning Calorimetry (DSC). As a result, we found that the conductivity of obtained poly[bvim][NTf2] is higher under confinement in comparison to both bulksynthesized polymer and unreacted monomer at some specific temperature conditions. This rather surprising and promising finding seems to indicate important remarks for future developments in the production of PILs-based materials characterized by desired and controlled conductivity. 2. EXPERIMENTAL SECTION 2.1. Materials 2,2′-Azobis(2-methylpropionitrile) (AIBN, 0.2 M solution in toluene) was purchased from the Sigma Aldrich. The nanoporous alumina oxide membranes used in this study were supplied from Synkera Co. Details concerning porosity, pore distribution, etc. can be found in Table 1 and at the web page of producer28. The filling ratio was calculated taking into account both: (i) the parameters of the applied temples and (ii) weight before and after infiltration procedure. It should be added that we assumed density of the confined material to be the same as bulk one. The chemical structures of the investigated monomer and applied initiator were presented in Scheme 1. The detailed information about the synthesis of the applied monomer can be found in Ref. 29.



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(a) H3C

(b)

+

N

N CH3

H3C N

N N

CH2 NTf 2

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-

CH3

CH3

N

AIBN

[bvim][NTf2]

Scheme 1. The chemical structure of the monomer (a) and initiator (b).

Parameter Pore diameter [nm] Pore density [cm-2] Pore period [nm] Estimated porosity [%] Filling ratio after the infiltration [%]

18 6·1010 44 15

55 6·109 143 13

80

85

Membranes 73 2·109 243 10

100 9·108 243 7

150 9·108 243 15

80

85

79

Table 1. Details concerning porosity, pore diameter and distribution of AAO membranes. 2.2. Samples preparation Ionic monomer [bvim][NTf2] (2.3 g, 5.3 mmol) was placed in a flask and purged with argon. AIBN in toluene (12.73 mg, 0.078 mmol) was transferred into the flask together with the AAO membrane (Prior to filling, AAO membranes were dried in an oven at 423 K under vacuum to remove any volatile impurities from the nanochannels). For all experiments the required amounts of AIBN as a catalyst was 0.5 %. Then, the whole system was maintained at T =293 K in vacuum (10-2 bar) for 24 h to let both compounds flow into the nanocavities. After completing the infiltration process, the surface of AAO membrane was dried and the excess sample on the surface removed by use of paper towel. In the experiment, we used membranes with a different pores diameter: 150, 100, 73, 55 and 18 nm. 2.3. Methods BDS measurements Dielectric permittivity ε*(ω) = ε’(ω)–iε”(ω) values at ambient pressure were measured by using the impedance analyzer (Novocontrol Alpha) over a frequency range from 1·10-1 to 6 ACS Paragon Plus Environment

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3·106 Hz. The samples were placed between two stainless-steel electrodes (diameter: 10 mm, gap: 0.1 mm) and mounted inside a cryostat. During the measurement, each sample was maintained under dry nitrogen gas flow. The temperature was controlled by Quatro Cryosystem using a nitrogen gas cryostat, with stability better than 0.1 K. The time dependent dielectric measurements were carried out at 363 K. Then, samples were measured on cooling from the reaction temperature down to 185 K. DSC measurements Calorimetric measurements of the isothermal reaction were carried out by Mettler-Toledo DSC apparatus equipped with a liquid nitrogen cooling accessory and an HSS8 ceramic sensor (heat flux sensor with 120 thermocouples). Temperature and enthalpy calibrations were performed by using indium and zinc standards. The sample was prepared in an open aluminum crucible (40µL) outside the DSC apparatus. The time dependent DSC measurements were carried out at 363 K. After the polymerization, samples were measured on heating from 273 K to 523 K at constant heating rate of 10 K/min. Each measurement at a given temperature was repeated 3 times. For each experiment a new sample was prepared. MALDI – TOF measurements Sample preparation: The template material (Al2O3) was treated with the solution of copper(I) chloride (CuCl) in hydrochloric acid (HCl). Subsequently, the AAO membrane was selectively dissolved in 5.0 % solution of phosphoric acid (H3PO4). This allowed to obtain organic nanostructures, which could be filtered from the above solution. Mass spectra were obtained on a Shimadzu AXIMA Performance MALDI–TOF mass spectrometer operated in linear mode. The laser power was optimized to obtain a good signalto-noise ratio after averaging 250 single-shot spectra. 2,5-dihydroxybenzoic acid (DHB, MDHB = 154.15 g/mol) was used as matrix substance (20,0 mg/mL, solution in THF), while



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polymer samples were dissolved in THF. 1,5 µL of the matrix solution was applied onto a stainless-steel target plate then air dried. Afterwards, 1,5 µL of the sample solution was spotted on a dry matrix surface and air dried for several minutes at room temperature. Data were acquired in linear mode with 250 profiles collected by laser firing and 5 shots accumulated into one profile. Data were obtained and analyzed using Shimadzu Biotech Launchpad program.

3. RESULTS AND DISCCUSION A. Monomeric Ionic Liquid Confined in AAO Membranes DSC thermograms recorded upon heating of quenched monomer confined within two AAO membranes of pore diameter 18 nm and 150 nm are presented in Fig. 1(a) and (b). As illustrated, two jumps in heat capacity, ascribed to the double glass transitions (Tgs), can be noticed30,31,32,33,34. In comparison to the bulk sample, where only one glass transition can be observed (see inset in Fig.1(a)). Accordingly to the two-layer model31, the lower transition, Tg1, is related to the core molecules located in the middle of the pores characterized by faster dynamics. It is mainly related to the loose packing of the molecules. The second, Tg2, which is higher than the glass transition of the bulk sample, is ascribed to the interfacial layer of molecules attached to the walls of the nanocavities31. The observed transitions are clearly confinement dependent and the difference between them (∆T=Tg2-Tg1) is seen to increase with reducing the size of pores. As presented in Fig. 1(c), the ∆T reaches value of 47 K and 24 K for monomer confined within the smallest (18 nm) and the largest (150 nm) nanocavities, respectively. It is worthwhile to stress that similar ∆T values were also reported for both 36 തതതതത PMMA (∆T = 45 K)35 and polypropylene glycol (PPG, ‫ܯ‬ ௪ = 4 000 g/mol, ∆T = 46 K)

confined in AAO membranes.


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Furthermore, in order to study the molecular dynamics as well as charge transport of the bulk and confined monomer, BDS technique has been employed. The representative dielectric spectra measured for [bvim][NTf2] incorporated into AAO membrane with a pore size of 18 nm are presented in Fig. 2(a) in electric modulus representation. It should be stressed that due to a strong rise in the imaginary part of permittivity, ε”, at low frequency from the huge contribution of dc conductivity, σdc, connected to the charge transport, the dielectric spectra of conductive materials are often analyzed in either modulus (M*) or conductivity (σ*) representation37,38,39,40, which are related according to the following equation41:

M * (ω) =

i2πfε 0 1 = , ε * (ω) σ * (ω)

(1)

In modulus representation (see Fig. 2(a)), collected spectra reveal the presence of two relaxation peaks, ascribed to (i) conductivity relaxation process located at higher frequencies and related to σdc of the examined systems and (ii) an additional one observed at lower frequencies, which presumably might be related to an interfacial process connected to the motion of molecules attached to the walls of the nanocavities42,43,44,45,46. As illustrated, both processes shift to the lower frequencies with decreasing temperature. On the other hand in conductivity representation (see Fig. 2(c)), three regimes can be distinguished: (i) the power law behavior at high frequencies, (ii) a plateau, on the intermediate frequency range, which directly yields σdc and (iii) the electrode polarization effect at lower frequencies, due to the accumulation of the ions at the sample-electrode surface41. It is worthwhile to add that dc conductivity of confined [bvim][NTf2] exhibits some frequency dependence, as shown in Fig. 2(c), which in the literature is discussed in the term of a varying distribution of pore diameter47,48. To analyze the molecular dynamics and charge transport behavior of [bvim][NTf2] within the examined nanosystems, the relaxation times, τ, of both processes were determined 9 ACS Paragon Plus Environment


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from the maximum of the peak observed in Fig. 2(a), where τ = 1/2πfmax

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41

. The obtained

values of τ were plotted versus 1000/T, as illustrated in Fig. 2(b) for monomer incorporated in AAO membranes with the pore diameter of 18 nm and 150 nm. For comparison, bulk data taken from Ref. 29 were also included. As shown, T–dependence of conductivity relaxation times, τdc, of confined samples differ significantly from their bulk counterpart in the entire range of studied temperatures. Interestingly at higher temperatures, the conductivity relaxation of confined monomer was found to be slower with respect to the bulk liquid. However, upon further cooling, the systematic enhancement of dynamics of this process in spatially restricted sample can be noted in the vicinity of the Tg. On the other hand, τdc of confined [bvim][NTf2] collapse perfectly onto one curve at high temperatures. However, at some temperature (labeled here as a crossover temperature, Tc, see dotted line in Fig. 2(b)), significant enhancement of conductivity relaxation for the sample confined in the smallest pores (d = 18 nm) with respect to the one infiltrated at larger pores is seen. Interestingly, Tc determined from dielectric data corresponds very well with Tg2 determined from DSC measurements, which, as one can recall, was assigned to the vitrification of the molecules attached to the walls (see dotted line in Fig. 2(b) and (d)). Therefore, one can suppose that the enhancement in dynamics of conductivity as well as charge transport in small pores is strictly related to the mobility of interfacial molecules. It should be stressed that presented herein results are consistent with the data reported for both low (i.e. salol33 or triphenyl phosphite 36 തതതതത (TPP34) and high (polypropylene glycol, ‫ܯ‬ ௪ = 4 000 g/mol ) molecular weight glass formers

confined within AAO membranes. In those samples, the sharp crossover in the molecular dynamics of the core molecules was also observed and discussed in the context of viftification of the interfacial molecules or polymers. Recent studies revealed that material frozen at the interface poses an additional constrain and system becomes quasi-isochoric. Consequently, a negative pressure develops in pores at such conditions49,50.


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Next, we analyzed also the temperature dependence of σdc. Due to the observed frequency dependence of conductivity in the spectral regime ascribed to σdc, its values were determined from σ’ at fc, according to the approach proposed by Iacobs et al.47. As one can recall the fc is equivalent to the frequency corresponding to the maximum of the peak in the imaginary part of M*41. Then, the obtained values of conductivity were recalculated according to the ‘active surface’ of examined material. It should be reminded that to evaluate properly σdc, porosity of AAO and surface occupied by monomeric ionic liquid has been taken into account (see Table 1). In addition, the filling ratio of applied materials was also considered. Determined values of σdc were further potted vs 1000/T, see Fig. 2(d). As illustrated, studied temperature dependences of σdc of the confined samples again varied from the bulk in the whole range of experimental data. Surprisingly at higher temperatures, the pronounced reduction of conductivity of [bvim][NTf2] confined in AAO pores can be noticed when compared to the bulk sample. However, decreasing temperature seems to reduce this difference. Therefore at further cooling, σdc(T) of examined nanomaterials cross the bulk counterpart and the enhancement of the charge transport can be detected in the vicinity of Tg. Herein, it should be stressed that slightly different scenario was observed in the case of 1butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) confined within porous SiO2 membranes with pore diameter in the range of 7.5 – 10.4 nm47. It was shown that conductivity of [bmim][BF4] nanomaterials collapses perfectly (within the experimental uncertainty) onto one curve with the bulk values at high temperatures. However, the lowering temperature revealed the systematic enhancement of σdc with increasing confinement. Such a discrepancy between our data and the ones reported by Iacob et al.47 can be related to the different properties of the host material, degree of confinement as well as strength of interactions between template and examined ionic liquid, which furthermore can significantly affect the charge transport within pores. In this context, it is worthwhile to mention recent studies



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(including molecular simulation) on ion transport in nanomaterials. It was reported that the ion diffusion might be either slowed down

51,52

or accelerated

47,53,54

due to the applied

nanoconfinement. The observed behavior is a counterbalance between many factors, i.e. the shape of ions and ions-wall interaction, among which the ion packing seems to be the most important 54. It was reported that the ion transport increases significantly with respect to the bulk for one layer of ions; while for larger systems (with more than one layer), the ion diffusion decreases independently to the state of charging indicating the importance of controlling the dimensionality of examined systems 54. In next step, temperature dependences of both relaxation processes identified in modulus representation have been fitted to the VFT equation55,56,57:  DT T0  T − T0

τ = τ ∞ exp 

  , 

(2)

where τ∞, DT and T0 are fitting parameters. The main aim of this procedure was to evaluate the glass transition temperatures of bulk and confined [bvim][NTf2], which were further plotted in Fig. 2(b). Note that Tg was defined as a temperature at which τint or τdc = 10 s. As shown, both Tgs obtained from the analysis of the relaxation peaks visible in modulus representation correspond quite well, within experimental uncertainty, with those estimated from DSC measurements. Such a good correspondence observed between higher glass transition temperature determined from DSC and from the analysis of the τ(T) of the slow relaxation process detected in modulus representation is a clear evidence that it is, in fact, related to the mobility of the interfacial molecules. Additionally as presented in the inset of Fig. 2(d), we tested also the Barton-NakajimaNamikawa (BNN) relation58,59,60 by plotting σdc versus ωc, where ωc=2πfc. As it can be observed, this relation holds over the entire range of examined herein data. It should be added


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that similar results were reported in case of a variety of bulk ionic liquids61, as well as [bmim][BF4] confined in SiO2 membranes47. B. Radical Polymerization Kinetics under Spatially Restriction Condition In order to obtain the polymerized ionic liquid within nanocavities of various pore diameter, the in situ nanopolymerization of the confined monomer was performed and monitored by means of DSC technique. Raw calorimetric data measured at isothermal conditions at T = 363 K are presented in Fig. 3(a). As it can be seen, the pronounced shift of the observed exothermic peak related to the polymerization to shorter times is detected, emphasizing the acceleration of the reaction with an increasing confinement. It should be mentioned that a similar effect can be also observed in case of increasing temperature for the bulk materials62,63,64,65. Utilizing standard procedure described in literature, additional nonisothermal DSC measurements were also carried out to estimate the degree of monomer conversion according to the following equation:

α DSC =

∆H (iso) , ∆H total

(4)

where αDSC is the conversion determined from DSC measurements, ∆H(iso) is the enthalpy change as a function of the polymerization time at given temperature, ∆Htotal is the total heat of the reaction. As reported widely in the literature, ∆Htotal = ∆H(iso)+∆H(non-iso) is the sum of enthalpies of the isothermal (∆H(iso)) and non-isothermal experiments (∆H(non-iso))66,67. Surprisingly, the αDSC was found to stay around 95% for all examined samples indicating strong influence of the AAO templates on the reactivity of monomeric ionic liquid. One can recall that depending on the properties of nanoporous material, the typical monomer conversion in case of radical polymerization varies in the range 40-85 %

14,15,23

. However

again, the observed discrepancies are strongly related to the properties of porous matrix.



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Next, the monomer conversion was plotted versus time (see Fig. 2 (b)) and fitted to the exponential function, that is characteristic for the first order kinetics to determine rate constants:

α = A ⋅ exp (− kt ) + C ,

(4)

where: α is the degree of reaction, k – rate of reaction, t – time, A – preexponential factor and C is an additional constant 68. The obtained values of k are presented as a function of the pore diameter in inset to Fig. 3(b). As shown, an increase of the pace of reaction with confinement is noted. One can recall that comparable results were also reported for various types of polymerization of different monomers polymerized within nanoporous templates15,19,69,70. In the majority cases, the observed enhancement of the reaction rate was explained in term of the catalytic effect of the surface hydroxyl groups attached to the pore walls. However, it should be stressed that similar results were also obtained for the step grow polymerization of bisphenol M dicyanate ester (BMDC) in hydrophobic silenized controlled pore glasses, CPG17. In this particular case, authors suggested also that the observed acceleration might be assigned to the increased number of collision of molecules near the surface due to reduced degree of freedom17. Nevertheless in case of free radical nanopolymerization of methyl methacrylate (MMA), observed acceleration of the reaction was explained to be a consequence of (i) reduced diffusivity of free radical active chains and (ii) nearly unaffected diffusivity of monomer69,70. In this context, one can mention very recent studies showing unexpectedly that free volume of the confined material is higher with respect to the bulk sample at given thermodynamic conditions71. Consequently, it is highly possible that even for the more viscous material produced upon polymerization, the space accessible for the monomers is still large enough to promote their diffusion and lead to the enhancement of the rate of the reaction. However, the acceleration of examined radical nanopolymerization of [bvim][NTf2] does not change monotonically with degree of confinement, see inset to Fig. 14 ACS Paragon Plus Environment

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3(b). It is well visible that below 55 nm some effect of saturation can be detected. Consequently, further increase in the degree of confinement does not affect the rate of the reaction. In contrast, one can recall recent paper by Salsamendi et al.20 on the radical polymerization of 1H,1H,2H,2H-perfluorodecyl acrylate (MFA) carried out within AAO templates, where the decrease in reaction rates compared to the bulk was observed. In this case, authors suggested that the observed decrease is connected with the increased termination step of the reaction due to lower effective volume experienced by the radicals under nanoconfinement conditions20. Hence to better understand observed experimental data and gain more insight into this issue further studies with the use of Positron Annihilation Lifetime Spectroscopy (PALS) are required. As complementary to the calorimetric studies, the progress of the polymerization has been also monitored by BDS technique. The application of this method allows to monitor time evolution of dc conductivity, σdc, which seems to be fundamental variable characterized conductive systems72. Furthermore, we decided to explore whether there is any relationship between this variable and the monomer conversion estimated from DSC measurements. In Fig. 4(a), dielectric data collected upon polymerization of [bvim][NTf2] in the 18 nm pores are presented in the conductivity representation. As mentioned before, two regimes can be distinguished: (i) the plateau at high frequencies related to the dc conductivity of the sample and (ii) the electrode polarization effect at lower frequencies that results from the accumulation of the ions at the sample-electrode interface. As can be observed, the formation of the polymer chains is accompanied with a decrease in dc conductivity. Although, it should be noted that this drop is not significant. In next step, kinetic curves have been constructed basing on the analysis of σdc accordingly to the following equation:

α dc σ (0) − σ (t ) = α max σ (0) − σ (∞)

(5) 15

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where αmax is the maximal conversion; while σ(0) and σ(∞)are the initial(monomer) and final(product) values of the conductivity measured upon reaction, respectively. Assuming that the monomer conductivity is unaffected during the polymerization. It was found that kinetics curves constructed from the dielectric data follow the exponential shape (data not shown), similarly as in case of calorimetric data. Therefore, to explore the relationship between the monomer conversion (from DSC measurements) and the variation of dc conductivity (from BDS studies), the αdc was plotted as a function of αDSC (see Fig. 4(b)). Surprisingly, obtained data collapsed onto one mastercurve in case of bulk and sample confined within 150 nm pores. In this case, the obtained data can be successfully approximated by a linear fit (s = 0.92). On the other hand, for the highest degree of confinement, the pronounced deviation from the linear dependence is noted, indicating more complex relationship between conductivity and progress of reaction in such systems. C. Polymerized Ionic Liquid (PIL) Obtained within AAO Membranes In Fig. 5(a), (b) and (c), representative DSC curves recorded for the samples measured before and after reaction carried out in bulk and under spatial restriction are presented. As illustrated, the collected data revealed again the presence of the double glass transition as well as the exothermic peak related to the residual heat of unreacted monomers. Values of both glass transition temperatures determined before and after the performed nanopolymerization are presented as a function of the pore size in Fig. 5(d). As can be observed, the Tg2 (connected to vitrification of the interfacial polymers) is much higher with respect to the unreacted monomer due to the formation of polymer chains. Moreover, its value differs only slightly as degree of confinement increases, indicating rather similar properties of the macromolecules produced at the pore walls. It should be also noted that this glass transition temperature is also significantly higher than the one determined for the bulk-synthesized poly[bvim][NTf2]. Thus, one can suppose that either strong interactions between obtained 16 ACS Paragon Plus Environment

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polymers and host matrix contributes to this phenomenon or polymers of higher molecular weights are synthesized at the interface. This issue will be clarified in the further part of this paper. Moreover, the Tg1 of obtained nanoPILs is significantly lower than the one obtained for the bulk-synthesized polymer. What is more, the glass transition temperature of confined poly[bvim][NTf2] is nearly the same (within experimental uncertainty) as the one determined for the unreacted monomer, indicating the possibility that polymerization did not occur at the center of the pores. Herein, one can mention studies on the samples confined within the various types of nanoporous materials32,33,34,35,36,73,74,75. Generally, the lowering of the glass transition temperature with increasing confinement is observed. In fact, the magnitude of depression of Tg was observed to be strictly related to the properties of nanoporous templates. We are strongly convinced that an increase in the glass transition related to the increasing chain length of the produced polymer is compensated by the finite size effect posed by the nanochannels. Consequently, the measured Tg1 remains unaffected by the progress of reaction. This hypothesis becomes even more probable taking into account DSC data, which showed that monomer conversion under confinements is around 95 %. Herein, it should be also mentioned that very similar results were reported in case of polycyanurate obtained in porous coordination glasses, PCG18. It was shown that lower Tg1 decreases with confinement, and this effect was assigned to the intrinsic size effect, as widely reported in the literature18,76,77,78. On the other hand, the higher Tg2 was noted to remain nearly constant. Further, dielectric measurements on the obtained poly[bvim][NTf2] confined in AAO templates were carried out in the wide range of temperature to examine molecular dynamics and charge transport in such materials. First, modulus spectra (Fig. 6(a)) were analyzed to determine conductivity relaxation time using the same procedure as described above in case of unreacted monomer. Determined τdc together with the ones estimated for the interfacial process were plotted vs reciprocal temperature in Fig. 6(b). Next, obtained dependences were



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Page 18 of 37

fitted to the VFT equation to determine the glass transition temperatures, which were furthermore depicted in inset to Fig. 5(b). Again, the Tg was defined as a temperature for which τ = 10 s. As can be observed, both Tgs determined from dielectric data agree very well with those estimated form DSC measurements (see inset of Fig. 6(b)). Next, the charge transport for poly[bvim][NTf2] confined in AAO membranes of given pore diameter has been studied. For this purpose, dielectric spectra were presented in conductivity representation, see Fig. 6(b). As illustrated, again two regimes corresponding to σdc and electrode polarization effect can be observed, both moving towards lower frequencies upon cooling. Note that values of dc conductivity were determined in the same way as in case of the unreacted monomer. For comparison, data for bulk monomer and polymer were also added. As displayed in Fig. 6(d), the confined poly[bvim][NTf2] has conductivity higher than the bulk-synthesized sample in the studied range of temperature. This result is quite expected in view of the data published in literature generally showing enhancement of σdc in spatially restricted ionic liquids47,48. It seems that this phenomenon originates from the interplay of few factors, i.e. the strength of interaction between host and guest molecules, geometry of confinements as well as free volume accessible for the ionic materials, which contributes to the change in the mechanism of ion conduction. Nevertheless, it should be highlighted that under certain thermodynamic conditions, conductivity of the poly[bvim][NTf2] synthesized under confinement is even higher in comparison to the one measured for the bulk monomer. What is important, our data indicated also that this effect can be controlled by the size of pores. In addition, the validation of BNN relation has been performed and found to be satisfied also in case of confined-synthesized polymers (see inset in Fig. 6(d)). Finally, produced polymer samples were analysed by means of MALDI-TOF MS, which is a soft ionisation technique and form mainly single charged species (see Fig. 7). The calculated mass of mer unit equals to 431.375 unit for [bvim][NTf2]. Due to the free radical 18 ACS Paragon Plus Environment

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polymerization (FRP) mechanism, the obtained polymer chains might be terminated with initiator (AIBN-fragment), proton or unsaturated double bond, as presented in Fig. 8. The representative spectrum of poly[bvim][NTf2] synthesized under confinement in AAO templates (d = 18 nm) is presented in Fig. 7(a). As illustrated, spectrum contains several signals with higher intensity, which is related to the low concentration of the sample derived from the template. In the recorded mass spectrum, one can distinguish series of peaks corresponding to sodium adducts [M+Na]+ of polymer chains with AIBN initiator fragment as starting group and H as terminal group, ranging from 950 to 2000 Da with n in the range 2 – 4 (i.e. for n = 2: Mcalc=954.846, Mobs= 957.4; for n = 3: Mcalc=1386.221, Mobs= 1382.3; for n = 4: Mcalc=1817.6, Mobs= 1818.3, Structure I, Fig. 8). Additionally, there are also signals from sodium adducts [M+Na]+ of copolymer chains containing both [bvim][NTf2] mer units and [bvim] mers deprived of both C4H9 substituent and the Tf2N- anion, labelled as [vim] units, connected with following series of peaks, i.e. for n = 4: 2[bvim][NTf2]:2[vim] Mcalc=1120.09, Mobs=1118.06; for n = 6: 3[bvim][NTf2]:3[vim] Mcalc=1668.56, Mobs=1667.2; for n = 7: 4[bvim][NTf2]:3[vim] Mcalc=2099.94, Mobs=2099.39; for n = 10: 7[bvim][NTf2]:3[vim] Mcalc=3394.06, Mobs=3397.05. It should be highlighted that accordingly to MALDI data presented in Fig. 7, Mw of confined-synthesized polymers is significantly higher with respect to the material recovered from the bulk reaction. As discussed above, this effect is discussed in the literature in term of the influence of limited space volume over reactivity of radicals formed during growth of the macromolecules. As reported, the diffusivity of the growing polymer chain with free radical active chains decreases with applied confinement, whereas the diffusivity of monomer is not significantly affected. Consequently, the rate of propagation relative to termination increases in nanosystems leading to higher molecular weight69,70. However, we think that the free volume of the confined materials (which was shown to be higher with respect to the bulk sample71) has also important influence on the progress of



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Page 20 of 37

polymerization (including the initial step of the reaction) as well as properties of the recovered polymers even in case of pores of larger diameter. Results discussed herein are very interesting and can be an important indication to develop new strategies of the production of nanoelectolytes materials with desired and controlled properties (i.e. conductivity) and significant commercial meaning. As mentioned before, PILs attracted attention of many scientific research group since they are hybrid materials sharing properties of ionic liquids (high conductivity) and macromolecules (solid materials easy to store and process). In fact, the enhancement of conductivity that drops upon polymerization of monomeric ionic liquid became a main aim of many investigations. Briefly, it is emphasized that the mobility, type of cation or anion, rigidity of the backbone, ability to form network, supramolecular structures, side chains as well as chemical structure of monomeric unit may significantly affect charge transport. Consequently, new ways of synthesis of these materials using well designed ionic liquid are currently developed, often complex and multistage. In this context, presented herein data clearly demonstrated that the enhancement of conductivity of PILs can be easily achieved just by carrying out polymerization of ionic liquid under geometrical confinement conditions. As a result, the nanosystem of higher conductivity with respect to the bulk-synthesized sample can be obtained, as presented in details above. Moreover, the enhancement in σdc can be controlled and adjusted by the variation of the pore size of nanoporous materials enabling production of materials of similar conductivity as starting ionic monomer. Also the analysis of Mw of the produced nanomaterials revealed a pronounced confinement dependence and indicated different physical and mechanical properties of confined-synthesised materials. Therefore, those materials can be easily applied, for instance as a replacement of a conventional liquid electrolytes use in case of lithium ion batteries, which often are volatile, flammable and limited due to safety restriction. Similar as in case of dye-sensitized solar cells (DSSC)


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challenging with leakage, dye desorption or electrode corrosion. A solution overcoming those problems might be exactly polymer-based nanomaterials (as studied herein). The application of PILs materials in electronic devices might both prevent problems and provide enhanced conductivity, high electrochemical stability, non-flammability, low cost and easy processing. 4. SUMMARY AND CONCLUSION In this paper, we studied the molecular dynamics and charge transport of the confined monomeric ionic liquid [bvim][NTf2] as a function of the pore diameter. Additionally, the kinetics of nanopolymerization of confined monomer was also studied and the charge transport of obtained poly[bvim][NTf2] under confinement was probed. It was demonstrated that the reaction accelerates with the degree of confinement. Although at highest confinement, some saturation effect can be visible. Currently, these observations are discussed in the context of the catalytic character of the porous template or decrease in diffusivity of the free radical active chains. Although here basing on the newest research, the variation of free volume is proposed to explain presented herein experimental data. Nevertheless, the catalytic impact of the applied templates cannot be neglected. Interestingly, we found that examined nanopolymerization is quite heterogeneous. Consequently, properties (molecular dynamics and glass transition temperatures) of materials recovered at the pore walls and in the middle of the pores differ significantly. Moreover, molecular weight of the confined-synthesized macromolecules is higher with the respect to their bulk counterpart. Finally, conductivity of produced poly[bvim][NTf2] under confinement was investigated. Surprisingly, the charge transport in these materials was found to be significantly enhanced and at some thermodynamic conditions it becomes even higher than σdc of starting materials. Those results are mainly promising in the context of future development of fabrication of PILs materials of desired properties and versatility of practical application, including nanotechnology. AUTHOR INFORMATION 21 ACS Paragon Plus Environment


Corresponding Author *(MT) [email protected], (KK) [email protected] Notes The authors declare no competing financial interests. ACKNOWLEDGEMENT K.K. and M.T. are thankful for a financial support from Polish National Science Centre within SONATA BIS 5 project (Dec 2015/18/E/ST4/00320). FIGURES

(c)

heating rate 10 K/min HF [a.u.] 160

Tg,inf

230

Tg,dc

Tg = 195 K 200

240

Tg1,DSC

220

280

Tg2,DSC

Tg2 = 232 K Tg1 = 185 K

Temp. [K]

(a) 18 nm 150

210

200

250

300

Temp. [K]

Tg [K]

Heat Flow [a.u.]

bulk [bvim][NTf2],

∆T18nm = 47 K

∆T150nm = 24 K

200

Heat Flow [a.u.]

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 22 of 37

(b) 150 nm 190

Tg2 = 216 K

bulk 180

Tg1 = 192 K 150

200

250

300

0

30

Temp. [K]

60

90

120 150 180 210 240

Pore diameter [nm]

Fig. 1. Panels (a) and (b) present DSC curves of the examined monomeric ionic liquid incorporated in AAO membrane with the pore diameter of 18 nm and 150 nm, respectively; As an inset in panel (a), DSC curve of bulk sample is presented. Panel (c): dependence of the glass transition temperatures vs pore diameter. The Tg of bulk material was taken from Ref. 29.


Page 23 of 37

(a) 18 nm

(b)0

conductivity relaxation process

interfacial process 100

10-1

T = 265 K T = 185 K ∆T = 10 K

decreasing temperature 10

0

1

10

2

10

10

3

10

4

10

5

-2 -3 -4 -5 -6

-8 6

10

interfacial process: 18 nm 150 nm conductivity relaxation process 18 nm 150 nm bulk VFT fits

-7

10-2 -1

decreasing temperature

-1

log10(τdc [s])

Modulus, M"

101

10

3.0

3.5

Freq. [Hz]

-10

10

-12

10

ing as e e r tur c de pera tem

-14

10

T = 330 K T = 185 K ∆T = 10 K

10-16

-log10(σ' [S/cm])

14

12

4.0

4.5

5.0

18 nm 150 nm linear fit

-8

log10(σ'[S/cm])

(d)

(c) 18 nm 10-8

18 nm 150 nm

1000/Temp. [1/K]

16

σ' [S/cm]

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


-10 -12 -14

s=1

-16 0

10

8

1

2

3

4

5

6

7

log10(ωc [1/s])

18 nm 150 nm bulk VFT fit

decreasing temperature

6

4 10-1

100

101

102

103

104

105

106

3.5

Freq. [Hz]

4.0

4.5

5.0

1000/Temp. [K-1]

Fig. 2. Panel (a): Dielectric spectra collected for the monomer confined within the AAO membranes of the smallest pore size presented in the modulus representation; Panel (b): The temperature dependence of the determined relaxation times. Panel (c): The temperature evolution of real part of conductivity spectra collected for the monomer confined within the nanocavities of the smallest pore size; Panel (d): The temperature dependence of –log10σdc. As an inset in panel (d), the plot of σdc vs ωc is presented (BNN relationship). Bulk data were taken from Ref. 29.



(a) at 363 K

1.0

(b) at 363 K 18 nm 150 nm bulk exponential fits

0.6 -2.8

-2.9

0.4

0.2

18 nm 150 nm bulk 0

3000

-3.0

-1

log10(k[s ])

conversion, αDSC

Heat Flow [a.u.]

0.8

0.0

-3.1

at 363 K

-3.2

DSC fit bulk

bulk

-3.3 0

40

80

120

160

200

Pore diameter [nm]

0

6000

3000

6000

Time [s]

Time [s]

Fig. 3. Panel (a): The raw isothermal DSC data; Panel (b): The time evolution of the monomer conversion determined from DSC measurements. As an inset in panel (b), the dependence of the polymerization rate constant vs pore diameter is presented. Bulk data were taken from Ref. 29. 10-6

(a) 18 nm at 363 K

(b)

dc conductivity

10-7

18 nm 100 nm 150 nm bulk linear fit

1.00

0.75

polarization of electrodes

progress of the reaction

αdc

σ' [S/cm]

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 24 of 37

0.50

s = 0.92

0.25

t=0s t = 8 700 s ∆t = 900 s

-8

10

1

10

2

10

3

10

4

10

5

10

0.00 6

10

0.00

Freq. [Hz]

0.25

0.50

αDSC

0.75

1.00


Page 25 of 37

Fig. 4. Panel (a): Conductivity spectra collected upon the radical polymerization of the examined monomer confined within the AAO membranes with a pore size of 18 nm; Panel (b): Dielectric conversion calculated from eq. (5) plotted vs monomer conversion determined from DSC. Bulk data were taken from Ref. 29.

(d)

before after the reaction Tg2 = 232 K Tg1 = 185 K Tg2 = 239 K

240

(a) 18 nm

Tg1 = 190 K

before after the reaction

Tg2 = 216 K

∆Tg,150nm = 48 K 220

∆Tg,18nm = 49 K

Tg [K]

Heat Flow [a.u.]

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Tg1 = 192 K

bulk

200

Tg2 = 241 K Tg1 = 193 K

(b) 150 nm

before the reaction: Tg1

180

Tg2

before after the reaction

Tg = 195 K

[bvim][NTf2] after the reaction: Tg1

160

Tg2

Tg = 214 K 150

200

250

300

350

(c) bulk 400

450

poly[bvim][NTf2] 140

500

0

50

100

150

200

Pore diameter [nm]

Temp. [K]

Fig. 5. Panels (a), (b) and (c): DSC curves recorded for the samples measured before and after reaction carried out in bulk and under spatial restriction (d=18 nm and d=150 nm); Panel (d): The glass transition temperatures of the obtained polymers under confinement plotted vs the pore diameter. Bulk data were taken from Ref. 29.



(a)

(b)

18 nm

interfacial proces: 18 nm conductivity relaxation process: 18 nm 150 nm poly[bvim][NTf2]

-1

0

10

log10(τdc[s])

-1

10

VFTfits

-3

-4

-5

240

Tg1,DSC 220

-6

T = 279 K T = 187 K ∆T = 8 K

Tg2,DSC

Tg [K]

Modulus, M"

-2

Tg,BDS Tg,inf

200

-7 180

0

-2

50

-1

10

0

10

1

10

2

10

3

10

4

10

5

10

6

10

100

150

200

Pore diameter [nm]

-8

10

1

2

3

4

5

1000/Temp. [K-1]

Freq. [Hz] 16

(d) 14

-log10(σ'[S/cm])

10-8

12

-10

10

-8

T = 359 K T = 263 K ∆T = 8K

-10 -11 -12 -13

-14

s=1

-15 0

10

10-12


-9

log10(σ'[S/cm])

(c) 18 nm

σ' [S/cm]

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 26 of 37

1

2

3

4

5

6

7

log10(ωc[1/s])

8

18nm 150 nm bulk: [bvim][NTf2]

6

poly[bvim][NTf2] VFT fits

10-14

4 10-1

100

101

102

103

Freq. [Hz]

104

105

106

3.0

3.5

4.0

4.5

5.0

5.5

1000/Temp. [K-1]

Fig. 6. Panels (a) and (c) : Modulus and conductivity spectra collected for poly[bvim][NTf2] obtained within the AAO membranes with pore size of 18 nm are shown; Panel (b): The temperature dependence of the relaxation times of PILs adsorbed to the pore walls and in the center of nanocavities. As an inset in panel (b), glass transition temperatures estimated from DSC and BDS studies are plotted vs pore diameter. Panel (c): The temperature dependence of –log10σdc. As an inset in panel (d), the plot of σdc vs ωc is presented (BNN relation). Bulk data were taken from Ref. 29.


Page 27 of 37

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(a)

(b)

Fig. 7. Panel (a): MALDI TOF spectra of poly[bvim][NTf2] obtained within AAO membranes with the 18 nm pore diameter at T = 363 K; inset: m/z range 800-2000; Panel (b): spectra of bulk sample, inset: m/z range = 1100-1650. Bulk data were taken from Ref. 29.

Fig. 8. Possible structures of macromolecules obtained after radical polymerization of 1-



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Page 28 of 37

butyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide under confinement.

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For Table of Contents use only

Polymerization of Monomeric Ionic Liquid Confined within Uniaxial Alumina Pores as a New Way of Obtaining Materials with Enhanced Conductivity

Magdalena Tarnacka*, Anna Chrobok, Karolina Matuszek, Sylwia Golba, Paulina Maksym, Kamil Kaminski*, Marian Paluch 16

14

12

-8

log10(σ'[S/cm])

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


-log10(σ'[S/cm])

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-9 -10 -11 -12 -13 -14

s=1

-15 0

1

2

3

4

5

6

7

log10(ωc[1/s]) 10

8

18nm 150 nm bulk: [bvim][NTf2]

6

poly[bvim][NTf2] VFT fits 4 3.0

3.5

4.0

4.5

5.0

5.5

1000/Temp. [K-1]


Polymerization of Monomeric Ionic Liquid Confined within Uniaxial

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