polymers

Article
Preparation and Characterization of Cellulose Acetate
Propionate Films Functionalized with Reactive
Ionic Liquids
Joanna Kujawa 1 , Edyta Rynkowska 1,2 , Kateryna Fatyeyeva 2 , Katarzyna Knozowska 1 ,
Andrzej Wolan 1 , Krzysztof Dzieszkowski 1 , Guoqiang Li 1 and Wojciech Kujawski 1, *
1 Faculty of Chemistry, Nicolaus Copernicus University in Toruń, Gagarina Street 7, 87-100 Torun, Poland
2 Normandie Université, UNIROUEN, INSA Rouen, CNRS, PBS, 76000 Rouen, France
* Correspondence: wkujawski@umk.pl; Tel.: +48-56-611-4315; Fax: +48-56-611-4526




Received: 23 June 2019; Accepted: 18 July 2019; Published: 20 July 2019


Abstract: 1-(1,3-diethoxy-1,3-dioxopropan-2-ylo)-3-methylimidazolium bromide (RIL1_Br), 1-(2-etoxy-2

-oxoethyl)-3-methylimidazolium bromide (RIL2_Br), 1-(2-etoxy-2-oxoethyl)-3 -methylimidazolium
tetrafluoroborate (RIL3_BF4) ionic liquids were synthesized. Subsequently, the dense cellulose
acetate propionate (CAP)-based materials containing from 9 to 28.6 wt % of these reactive ionic
liquids were elaborated. Reactive ionic liquids (RILs) were immobilized in CAP as a result of the
transesterification reaction. The yield of this reaction was over 90% with respect to the used RIL. The
physicochemical properties of resultant films were studied using nuclear magnetic resonance (NMR),
scanning electron microscopy (SEM), energy dispersive X-ray (EDX), atomic force microscopy (AFM),
and thermogravimetric analysis (TGA). The RIL incorporation influenced the morphology of films by
increasing their surface roughness with the rise of RIL content. The thermal stability of CAP-based
membranes was dependent on the nature of the ionic liquid. Nevertheless, it was proven that CAP
films containing RILs were stable up to 120–150 ◦ C. Transport properties were characterized by water
permeation tests. It was found that the type and the amount of the ionic liquid in the CAP matrix
substantially influenced the transport properties of the prepared hybrid materials.

Keywords: polymer membranes; cellulose acetate propionate; reactive ionic liquid; transesterification
reaction; material characterization; water transport

1. Introduction
Polymer-based membranes have been elaborated for a range of applications, such as
biomaterials [1], electrolytes in fuel cells [2], sensors [3], and selective barriers exploited in separation
of gas and liquid mixtures (pervaporation, gas separation, reverse osmosis, nano-, ultra-, and
micro-filtration) [4,5], as well as for the recovery of metal ions [6]. The design and preparation of a
polymeric membrane material with an improved or novel characteristic has been driving the current
research in membrane technology [6]. There are various approaches studied, such as the use of
polymeric blends, membrane surface modification, membrane cross-linking as well as utilization of the
inorganic (e.g., carbon nanotubes—CNTs, metal organic frameworks—MOFs, zeolites) or organic (e.g.,
ionic liquids—ILs) additives for membrane preparation [7–10]. Membrane technology is known as
energy capable, environmentally approachable, and easy to scale-up, with a large outlook of expanding
its utilization with the growing need of employing more sustainable industrial processes. During the
design of the membrane material, its selectivity/permeation characteristics have been adjusted and
optimized for quite diverse separation tasks. Nevertheless, the membrane fabrication itself could be
much more sustainable and greener. To meet that requirement, two aspects of membrane production

Polymers 2019, 11, 1217; doi:10.3390/polym11071217 www.mdpi.com/journal/polymers

Polymers 2019, 11, 1217 2 of 23

have to be taken into account: the membrane material and the manufacture process [11]. Concerning
the green membrane material, the cellulose is one of the best candidates [12]. However, cellulose
can barely be dissolved in common solvents because of strong hydrogen bonds and crystallinity.
Chemically modified cellulose in the form of cellulose acetate has been successfully applied in a large
scale, for example as planar flat-sheet membranes for forward osmosis and as hollow fibers for seawater
desalination by reverse osmosis processes [11].
ILs have drawn special attention from the researchers due to their remarkable properties such as
negligible vapor pressures, and high thermal and chemical stability [13]. IL has also been considered
as a green solvent [14]. IL is a salt consisting of an organic cation and inorganic/organic anion,
possessing a melting point usually below 100 ◦ C [13]. The significant advantage of ILs is the possibility
to change their physicochemical properties by altering the cation and anion [15]. Ionic liquids can
be classified into two major groups: aprotic and protic ILs [16]. Properties of a given ionic liquid
such as hydrophilicity-lipophilicity, viscosity, surface tension, and density depend on the type of
cation and anion. Ionic liquids have been examined as a component of a polymeric matrix or
polymerization media [17]. The polymer modification with IL was found as a useful method to obtain
novel membrane materials with unique composition and material features or good transport and
separation properties [18,19]. Membranes containing ILs were successfully utilized for the recovery of
alcohols [20], separation of gases [21,22], and as separators in fuel cells [23] or lithium batteries [24].
An increasing interest in the elaboration of the polymeric membranes containing ILs has
been widely reported in the literature [2,25–29]. Guo et al. [30] used 1-alkyl-3-methylimidazolium
hexafluorophosphate as a plasticizer. Results showed that (C8MIM)(BF4) could successfully replace
the traditional molecular plasticizer. The incorporation of ionic liquids also improved permeability [30].
The selection of ILs for the preparation of polymer-IL system in which IL is firmly linked to the
polymer matrix is a key challenge, and it depends on the compatibility and the ratio between the
IL and polymer [2,31]. IL can be incorporated into the membrane material by mixing the polymer
with IL in a suitable solvent prior to the membrane formation [2]. Murakami et al. [32] pointed
out that functionalization of cellulose with the polymerizable ionic liquid (PIL) followed by the in
situ polymerization results in the interpenetrating polymer-IL network. Another approach to the
immobilization of IL is soaking of a native dense or porous polymer matrix with the solution of IL [33].
However, the development of ionic liquids utilization in membrane processes requires solving the
problem of ionic liquids leaching [34,35]. Ionic liquids were also incorporated into a membrane matrix
in order to increase the membranes stability [36]. Based on the scientific literature, it was found that
by addition of ionic liquid, mechanical and thermal stabilities were improved [37,38]. Stability of
this type of the membrane depends on the properties of ionic liquid, type of membrane support,
and interfacial tension between the membrane support and aqueous phase. Some researchers found
that IL can be lost from the membrane. This phenomenon was studied by Zhao et al. [39], and the
authors pointed out that two parameters have an impact of the mechanism of the IL loss: membrane
compression and ionic liquid extrusion from the membranes possessing large pores. The limit value of
pore size that ensures the stability of the material and avoids liquid losses were placed in the range of
100–200 nm [39]. The mentioned mechanism was defined based on the data for membrane prepared
with 1-n-butyl-3-methylimidazolium tetrafluoroborate ((bmim)(BF4)) immobilized in the following
matrices: polyvinylidene fluoride (PVDF), nylon 6 (N6), and polyethersulfone (PES) microporous
membranes. The promising approach to the stable polymer-IL system elaboration is the chemical
grafting of IL onto the polymer [40]. Hassan Hassan Abdellatif et al. [40] proposed the sequential
synthesis route for IL grafting onto cellulose acetate (CA) in order to minimize the leaching of IL as
well as to enhance the membrane performance in the ethyl tert-butyl ether (ETBE) purification using
pervaporation. Researchers reported the successful modification of CA with IL containing bromide
anion and various cations (imidazolium, pyridinium, and ammonium) confirmed by 1H nuclear
magnetic resonance (NMR) analysis. Moreover, the diminished release of IL from the membrane
due to the covalent bonds between IL and CA was pointed out. CA-based membranes chemically
Polymers 2019, 11, 1217 3 of 23

modified with ammonium-based IL revealed the highest performance in the pervaporative separation
of the ethanol-ETBE mixture at 50 ◦ C among all tested membranes. The obtained flux was equal to
0.182 kg m-2 h-1 for the membrane thickness of 5 µm [40]. A preparation of ionic gels is another
approach to improve the stability of ionic liquid in the membrane matrix. In this type of materials, the
ILs are immobilized in the swollen polymer matrix [41,42]. However, gas separation tests showed
that ionic gels were damaged during experiments under the influence of applied pressure [41]. The
promising method to minimize the IL leakage challenge is also a formation of membrane based
on the chemical modification of polymer with reactive ionic liquid (RIL) proposed in our previous
work [43]. The used ester-functionalized RILs consist of cations with ethoxy groups that can react
with the acetate or propionate substituents in CAP based on transesterification reaction creating
covalent bonds between RILs and polymer. Rynkowska et al. [43] elaborated CAP-based membranes
containing 3-(1,3-diethoxy-1,3-dioxopropan-2-yl)-1-methyl-1H-imidazol-ium bromide and used for
pervaporative dehydration of 2-propanol. The pervaporation results showed that introduction of RIL
into a membrane matrix improves the separation properties of CAP-based membranes. Moreover, the
RIL incorporation increases the membrane mechanical properties comparing to native CAP membrane
and CAP membranes with commercial plasticizers (TBC—tributyl citrate and ATBC—acetyl tributyl
citrate). CAP-RIL membranes showed also higher elongation at break in contrast with CAP-TBC and
CAP-TBAC membranes [43].
The main aim of this work is related to the chemical modification of cellulose
acetate propionate (CAP)-based membranes using reactive ionic liquids (RILs) containing
imidazolium cation, in order to fabricate the polymer material with immobilized IL. The
following RILs were used: 1-(1,3-diethoxy-1,3 -dioxopropan-2-ylo)-3-methylimidazolium bromide
(RIL1_Br), 1-(2-etoxy-2-oxoethyl)-3-methylimidazolium bromide (RIL2_Br), 1-(2-etoxy-2-oxoethyl)-3
-methylimidazolium tetrafluoroborate (RIL3_BF4). The imidazolium cation was chosen due to its
feasibility and good compatibility with CAP [44,45]. On the other hand, the anions were selected
based on the variation in their hydrophobicity/hydrophilicity properties. The novelty of this work
was the formation of membrane materials containing ionic liquids firmly linked to the polymer
matrix. Furthermore, to have deeper insight into the comprehensive analysis, the physicochemical and
material properties were determined using the various spectroscopic and microscopic techniques. The
determined features were subsequently referred to the transport performances of elaborated materials.

2. Materials and Methods

2.1. Reagents
The polymer films were prepared using cellulose acetate propionate (CAP-482-20; Eastman, USA;
MW = 75,000 g mol-1, where MW is polystyrene-equivalent molecular weights determined using size
exclusion chromatography) with acetyl, propionyl, and hydroxyl group content equal to 1.3, 48.0, and
1.7 wt %, respectively (Figure 1). N-methylimidazole (Sigma-Aldrich, Poland), ethyl bromoacetate
(Sigma-Aldrich, Poland), sodium tetrafluoroborate (Avantor Performance Materials Poland S.A.,
Poland), diethyl 2-bromomalonate (abcr GmbH, Karlsruhe, Germany) were used to synthesize RILs.
Solvents chloroform, diethyl ether, acetone delivered by Avantor Performance Materials Poland
S.A. (Gliwice, Poland) were used as received. Reverse osmosis (RO) deionized water (15 MΩ·cm)
was utilized within this study. Methanol and water of Honeywell liquid chromatography-mass
spectrometry (LC-MS) grade were used in LC-MS analysis.
 Polymers2019,
Polymers 11,x1217
2019,11, FOR PEER REVIEW 44ofof23
23
Polymers 2019, 11, x FOR PEER REVIEW 4 of 23

Figure 1. Chemical structure of cellulose acetate propionate (CAP).

Figure 1. Chemical structure of cellulose acetate propionate
propionate (CAP).
(CAP).
2.2. Reactive Ionic Liquids (RILs) Synthesis
2.2. Reactive Ionic
2.2. Reactive Ionic Liquids
Liquids (RILs)
(RILs) Synthesis
Synthesis
2.2.1.
2.2.1.1-(1,3-Diethoxy-1,3-Dioxopropan-2-ylo)-3-Methylimidazolium
1-(1,3-Diethoxy-1,3-Dioxopropan-2-ylo)-3-MethylimidazoliumBromide Bromide(RIL1_(RIL1_Br) Br)
2.2.1. 1-(1,3-Diethoxy-1,3-Dioxopropan-2-ylo)-3-Methylimidazolium Bromide (RIL1_ Br)
N-methylimidazole
N-methylimidazole(0.80 (0.80mL;
mL; 10 10
mmol), chloroform
mmol), chloroform (10 mL), and diethyl
(10 mL), 2-bromomalonate
and diethyl 2-bromomalonate (1.70
mL; N-methylimidazole
10 mmol) were added (0.80
to amL;
50 10 mmol),
mL chloroform
round-bottom flask (10under
mL), and
an diethyl
argon 2-bromomalonate
atmosphere and (1.70
heated
(1.70 mL; 10 mmol) were added to a 50 mL round-bottom flask under an argon atmosphere and heated
mL; 10 mmol)
under wereh.added to a 50 mL round-bottom flask under an argon atmosphere and heated
underreflux
refluxfor
for 2424 h. Subsequently,
Subsequently,chloroform
chloroformwas wasremoved
removedusing usingaarotary rotaryevaporator,
evaporator,and andthe the
under
remainingreflux for
yellow 24 h.
liquid Subsequently,
was washed chloroform
three times was
with 20removed
mL of using
diethyl a rotary
ether. Theevaporator,
residues and
of usedthe
remaining yellow liquid was washed three times with 20 mL of diethyl ether. The residues of used
remaining
solvents yellow liquid was washed three times with 20 mL of diethyl ether. The residues of used
solventswere
wereremoved
removedunder undervacuum
vacuum(66.7(66.7Pa)
Pa)during
during55h. h.The
Theyield
yieldofofRIL1_Br
RIL1_Brsynthesis
synthesiswas wasequal equal
solvents
to 98.8%, were
and removed
its structure under vacuum
(Figure 2A) (66.7
was Pa) during
confirmed 5
by h. The
NMR yield
analysisof RIL1_Br
[43]. 1H synthesis
NMR wasMHz,
(400 equal
to 98.8%, and its structure (Figure 2A) was confirmed by NMR analysis [43]. 1H NMR (400 MHz,
to 98.8%,
Bruker and its structure (Figure 2A) was confirmed by NMR analysis [43]. 1H NMR (400 MHz,
BrukerAvance
Avance III spectrometer,CDCl3)
III spectrometer, CDCl3)δδppm ppm10.55
10.55(s,(s,1 1H),
H), 7.83
7.83 (t, (t,
J =J 1.8
= 1.8
Hz,Hz, 1 H),
1 H), 7.587.58
(t, J(t,= J1.8
= 1.8
Hz,
Bruker
Hz, 1 H),Avance
7.07 (s, III
1 spectrometer,
H), 4.34 (dqt, J CDCl3)
= 15.9, δ ppm
7.1, 3.7 10.554 (s,
Hz, H), 14.13
H), (s,
7.833 (t,H), J 1.33
= 1.8(t,
Hz,J =17.2
H),Hz,
7.586 (t,
H). J 13C
= 1.8
1 H), 7.07 (s, 1 H), 4.34 (dqt, J = 15.9, 7.1, 3.7 Hz, 4 H), 4.13 (s, 3 H), 1.33 (t, J = 7.2 Hz, 6 H). 13C NMR
Hz, 1(101
NMR H), MHz,
7.07 (s,CDCl3)
1 H), 4.34ppm(dqt, J = 15.9, 7.1, 3.7 Hz, 122.99,
4 H), 4.13 (s, 3 H), 1.33 (t, J = 7.2 Hz, 6 H). 13C
(101 MHz, CDCl3) δ ppmδ 163.11, 163.11,
138.42,138.42,
123.24,123.24,
122.99, 64.16,64.16,
62.93,62.93,
37.12,37.12,
13.90.13.90.
NMR (101 MHz, CDCl3) δ ppm 163.11, 138.42, 123.24, 122.99, 64.16, 62.93, 37.12, 13.90.

Figure
Figure 2.
2. Chemical
Chemical structure
structure of
of (A) 1-(1,3-diethoxy-1,3-dioxopropan-2-ylo)-3-methylimidazolium
(A) 1-(1,3-diethoxy-1,3-dioxopropan-2-ylo)-3-methylimidazolium
Figure
bromide 2. Chemical
bromide(RIL1_Br), structure of (A) 1-(1,3-diethoxy-1,3-dioxopropan-2-ylo)-3-methylimidazolium
(B) 1-(2-etoxy-2-oxoethyl)-3-methylimidazolium
(RIL1_Br), (B) 1-(2-etoxy-2-oxoethyl)-3-methylimidazolium bromide (RIL2_Br),
bromide and (C) 1-(2-
(RIL2_Br), and
bromide (RIL1_Br), (B) 1-(2-etoxy-2-oxoethyl)-3-methylimidazolium
(C) 1-(2-etoxy-2-oxoethyl)-3-methylimidazolium
etoxy-2-oxoethyl)-3-methylimidazolium tetrafluoroborate
tetrafluoroborate bromide (RIL2_Br), and (C) 1-(2-
(RIL3_BF4).
(RIL3_BF4).
etoxy-2-oxoethyl)-3-methylimidazolium tetrafluoroborate (RIL3_BF4).
2.2.2.1-(2-Etoxy-2-Oxoethyl)-3-Methylimidazolium
2.2.2. 1-(2-Etoxy-2-Oxoethyl)-3-MethylimidazoliumBromide Bromide(RIL2_Br)
(RIL2_Br)
2.2.2. 1-(2-Etoxy-2-Oxoethyl)-3-Methylimidazolium Bromide (RIL2_Br)
Ethylbromoacetate
Ethyl bromoacetate(1.67 (1.67g;g;10
10mmol)
mmol)was wasadded
addedcarefully
carefullytotothe the25 25mLmL round-bottom
round-bottomflask flask
containing a solution
Ethylabromoacetate
containing of n-methylimidazole
(1.67 g; 10 mmol)
solution of n-methylimidazole (0.82 g; 10
wasg;added
(0.82 mmol)
10 mmol) in
carefully chloroform
to the 25
in chloroform (10
(10mL mL) and
mL)round-bottomheated
and heated under under
flask
reflux for
containing 24
a h. Subsequently,
solution of chloroform
n-methylimidazole was
(0.82 removed
g; 10 mmol)using
in a rotary
chloroform evaporator,
reflux for 24 h. Subsequently, chloroform was removed using a rotary evaporator, under vacuum (0.1 (10 mL) and under
heated vacuum
under
(0.1
Pa) Pa)for
reflux
duringduring
24
6 h. 6 h.yield
h. The The yield
Subsequently, of RIL2_Br
chloroform
of RIL2_Br synthesis
was
synthesis removed wasusing
was equal equal ato
to 96.4%, 96.4%,
rotary and
andevaporator,
its its structure
structure under
(Figure (Figure
vacuum2B) was2B)
(0.1
was confirmed
Pa) during
confirmed by6 h.NMRby
TheNMR
yieldanalysis.
of RIL2_Br
analysis. 1H NMR1H NMR(700 (700
synthesis
MHz, MHz,
was CDCl3)
equal
CDCl3) to δ ppm
96.4%,
δ ppm 10.17
and
10.17 its1(s,
(s, 1 H),
7.637.63
structure
H), (Figure
(t, =2B)
J(t,= J1.8 1.8
Hz, Hz,
was
1
1 H), 7.48
confirmed (t,
by J = 1.8
NMR Hz, 1 H),
analysis. 5.48
1H (s,
NMR2 H), 4.07
(700 (s,
MHz, 3 H), 4.25
CDCl3) (q,
δ J
ppm= 7.1 Hz,
10.17 2
(s,H),
1 1.30
H), (t,
7.63
H), 7.48 (t, J = 1.8 Hz, 1 H), 5.48 (s, 2 H), 4.07 (s, 3 H), 4.25 (q, J = 7.1 Hz, 2 H), 1.30 (t, J = 7.2 Hz, 3 H).J =
(t, 7.2
J = Hz,
1.8 3
Hz,H).
1
13C
13C NMR
H), NMR (176
7.48 (t,(176
J = 1.8MHz,
MHz, CDCl3)
Hz,CDCl3) δ
1 H), 5.48 ppm 165.69,
(s, 2165.69,
δ ppm H), 4.07138.08, 123.44,
(s, 3 H),
138.08, 122.52,
4.25 122.52,
123.44, (q, J = 7.162.60, 49.95,
Hz, 49.95,
62.60, 36.52,
2 H), 1.30 13.67.
(t,13.67.
36.52, J = 7.2 Hz, 3 H).
13C NMR (176 MHz, CDCl3) δ ppm 165.69, 138.08, 123.44, 122.52, 62.60, 49.95, 36.52, 13.67.
Polymers 2019, 11, x FOR PEER REVIEW 5 of 23

Polymers 2019, 11, 1217 5 of 23

2.2.3. 1-(2-Etoxy-2-Oxoethyl)-3-Methylimidazolium Tetrafluoroborate (RIL3_BF4)
A 50 mL flask was charged with 1-(2-etoxy-2-oxoethyl)-3-methylimidazolium bromide
2.2.3. 1-(2-Etoxy-2-Oxoethyl)-3-Methylimidazolium Tetrafluoroborate (RIL3_BF4)
(RIL2_Br) (1.25 g; 5 mmol) and acetone (30 mL). Subsequently, sodium tetrafluoroborate (0.55 g; 5
mmol) was
A 50 mL added, and charged
flask was the resultant
with solution was stirred at ambient temperature for
1-(2-etoxy-2-oxoethyl)-3-methylimidazolium 24 h. The
bromide white
(RIL2_Br)
crystalline
(1.25 g; 5 mmol)precipitate of sodium
and acetone (30 mL). bromide was filtered.
Subsequently, sodiumAcetone was removed
tetrafluoroborate using
(0.55 g; 5 mmol)a rotary
was
evaporator under vacuum (0.1 Pa) during 5 h. The yield of RIL3_BF4 synthesis
added, and the resultant solution was stirred at ambient temperature for 24 h. The white crystalline was equal to 76.5%,
and its structure
precipitate (Figure
of sodium 2C) was
bromide wasconfirmed
filtered. by NMR analysis.
Acetone was removed 1H NMRusing (700 MHz, evaporator
a rotary DMSO-d6) δunder ppm
9.08 (d, J (0.1
vacuum = 0.4Pa)Hz,during
1 H), 7.73
5 h.(dt,
TheJ =yield
6.2, 1.7 Hz, 2 H), 5.24
of RIL3_BF4 (s, 2 H),
synthesis 4.20
was (q, J =to7.1
equal Hz, 2and
76.5%, H), its
3.91structure
(s, 3 H),
1.24 (t, J2C)
(Figure = 7.1was Hz, 3 H). 13C
confirmed byNMR
NMR(176 MHz,1H
analysis. DMSO-d6)
NMR (700δMHz, ppm DMSO-d6)
166.95, 137.79, δ ppm122.78, (d, J = 0.4
9.08 123.49, 61.98,
Hz,
149.60, 36.08,
H), 7.73 J = 6.2, 1.7 Hz, 2 H), 5.24 (s, 2 H), 4.20 (q, J = 7.1 Hz, 2 H), 3.91 (s, 3 H), 1.24 (t, J = 7.1 Hz,
(dt,14.07.
3 H). 13C NMR (176 MHz, DMSO-d6) δ ppm 166.95, 137.79, 122.78, 123.49, 61.98, 49.60, 36.08, 14.07.
2.3. Preparation of Cellulose Acetate Propionate-Reactive Ionic Liquids (CAP-RILs) Films
2.3. Preparation of Cellulose Acetate Propionate-Reactive Ionic Liquids (CAP-RILs) Films
The 10 wt % CAP polymer solution was prepared as follows: 10 g of cellulose acetate propionate
powder 10
The was wtdissolved
% CAP polymer
in 90 solution was prepared
g of chloroform, and asthe
follows:
obtained10 g mixture
of cellulosewasacetate
stirredpropionate
at room
powder
temperaturewas dissolved
(21 °C ± in 90 gduring
3 °C) of chloroform,
24 h in and
order theto
obtained
obtain mixture was stirredsolution.
the homogenous at room temperature
The various
(21 ◦ C ± 3 ◦ C) during 24 h in order to obtain the homogenous solution. The various amounts of
amounts of RILs (9; 16.7; 23; and 28.6 wt % of RILs with respect to CAP content) were mixed with the
RILs
CAP solution23;
(9; 16.7; in and 28.6 wt %atofthe
chloroform RILsroom
with temperature
respect to CAP content)
during 24 were mixed this
h. During withtime,
the CAP the
solution in chloroform
transesterification at thebetween
reaction room temperature
CAP and RILs during 24 place
took h. During this3),
(Figure time, the was
which transesterification
subsequently
reaction
confirmed between
by theCAP NMRand RILs took place
analysis. The(Figure 3), which was subsequently
transesterification reaction occurredconfirmedbetween
by the NMR the
analysis. The transesterification reaction occurred between the propanoyloxymethyl
propanoyloxymethyl group in CAP and 2-etoxy-2-oxoethyl in RIL. The transesterification reaction group in CAP
and 2-etoxy-2-oxoethyl
starts by the protonation in RIL. The
of the transesterification
carbonyl group by the reaction
acid starts by the
protons, thus protonation
activating of it the carbonyl
towards the
group by the acid protons, thus activating it towards the nucleophilic
nucleophilic attack. Then, the carbonyl group undergoes the nucleophilic attack by the CAP attack. Then, the carbonyl
group undergoes
molecule. the nucleophilic
Subsequently, the protonattack by the takes
transfer CAP molecule.
place. TheSubsequently, the protonfrom
charge displacement transfer
the takes
–OH
place.
group Theto –O+ charge displacement
results from the
in the removal –OHethanol
of the group to –O+ results
molecule. in the
Finally, theremoval of the ethanol
deprotonation of the
molecule. Finally, the
resultant molecule deprotonation
occurs and the finalofproduct
the resultant molecule occurs and
of the transesterification the final
reaction product(Figure
is obtained of the
transesterification
3). reaction is obtained (Figure 3).

Figure 3. Scheme of the transesterification reaction between CAP and RIL2_Br.

RIL2_Br.

The
The polymer-RIL
polymer-RIL solution
solution was
was poured
poured onto
onto aa glass
glass Petri
Petri dish
dish and
and placed
placed under
under the
the hood
hood at
at
ambient temperature. CAP-RIL dense films were prepared by applying the phase inversion
ambient temperature. CAP-RIL dense films were prepared by applying the phase inversion method method
(i.e.,
(i.e., precipitation
precipitationby
bysolvent
solventevaporation)
evaporation)[46].
[46].CAP-RIL
CAP-RILfilms
filmswere left
were forfor
left solvent evaporation
solvent upup
evaporation to
48 h in order to obtain dry film samples.
to 48 h in order to obtain dry film samples.

2.4. Characterization of CAP-RILs Films

The 1H NMR and 13C NMR spectra of CAP-RIL films were recorded on a 400 MHz Bruker
Avance III or 700 MHz Bruker Avance III spectrometer (Bruker, Rheinstetten, Germany) at 25 ◦ C using
DMSO-d6 as a solvent.
Polymers 2019, 11, 1217 6 of 23

The distribution of chemical elements was studied using a scanning electron microscopy (SEM)
microscope (LEO 1430 VP, LEO Electron Microscopy Ltd. Cambridge, UK) with an energy dispersive
X-ray (EDX) spectrometer (Quantax 200, Bruker AXS Microanalysis GmBH, Germany; with EDX
detector XFlash 4010, Bruker AXS Microanalysis GmBH, Germany) at 28 kV. EDX analysis was
accomplished for non-sputtered samples. The morphology of the obtained CAP-RIL films was studied
by SEM microscope (Quanta 3D FEG) at 30 keV. In that case, prior to SEM analysis, film samples were
sputtered with a conductive layer of Au/Pd (80/20 composition) with the thickness equal to 2–6 nm. To
obtain a cross-section, the samples for SEM and SEM-EDX analysis were prepared by fracturing the
films in liquid nitrogen.
The surface topography of CAP-RIL films was also studied using an atomic force microscope
(AFM) with a NanoScope MultiMode SPM System and NanoScope IIIa and Quadrex controller (Veeco,
Digital Instrument, UK). The average roughness parameter (Ra) was evaluated based on a tapping
mode for the scanned sample area of 10 µm × 10 µm using Nanoscope v6.13 software (Veeco, Digital
Instrument, UK). At least three measurements per tested sample were performed in order to obtain
reproducibility of the results.
Contact angles for the investigated membranes were measured by implementation of goniometric
technique (Attention Theta from Biolin Scientific, Gothenburg, Sweden) using the sessile drop method.
Measurements were performed for water as a liquid after 5 s of equilibration at room temperature.
The thermal stability of CAP-RIL films was tested using a thermogravimetric analyzer TGA Q 500
(TA Instruments, USA) from 25 ◦ C to 800 ◦ C under the nitrogen atmosphere (heating rate 10 ◦ C/min
and nitrogen flow rate 90 mL/min).

2.5. Conversion Degree of RIL

The exact yield of the reaction between CAP and RIL was determined by applying the following
procedure using an LC-MS system. This device was chosen due to the greater sensitivity in relation
to NMR spectroscopy. Weighed pieces of studied membranes were sonicated with 2000 µL of water
for 20 min. 20 µL of the obtained solutions were diluted with 1500 µL of methanol and examined
using LC-MS system, measuring the area of the 241 m/z peak in positive selected ion monitoring (SIM)
mode. Shimadzu Liquid Chromatograph Nexera-i LC-2040C 3D Plus coupled with Shimadzu Mass
Spectrometer LCMS-2020 was used in this experiment. Moreover, Phenomenex Kinetex 2.6 µm C18
100A 50 × 4.60 mm chromatographic column was used in order to reduce a potential interference
impact and a noise value.

2.6. Water Permeation Tests

Water permeation measurements were performed at 25 ± 1 ◦ C implementing a laboratory-made
experimental rig (Figure 4). Prior to the tests, the membrane sample (active area of the membrane
2.5 cm2 ) was sealed in the permeation cell and dried by circulating nitrogen (Alphagaz 2, Air Liquide® ,
Paris, France) on both sides of the film until the lowest constant value of dew point (referred to the
lowest amount of moisture in the system) was reached (ca. −70 ◦ C). Then, liquid water (used as a feed)
was injected into the upstream compartment while the downstream compartment was continuously
swept out by the stream of dry nitrogen. Because of the differences in water activities on both sides of
the membrane, water molecules diffused across the membrane. The amount of vapor transported into
the downstream compartment was monitored by using a chilled mirror hydrometer (General Eastern
Instrument, Elcowa® , Mulhouse, France) connected to the data acquisition system. The experiments
were done at water vapor activities of feed stream increasing up to the saturation vapor pressure. The
data were collected until the system reached the stationary state.
Polymers 2019, 11, 1217 7 of 23
Polymers 2019, 11, x FOR PEER REVIEW 7 of 23

Figure 4. Scheme of water permeation setup.

Figure 4. Scheme of water permeation setup.
3. Results
3. Results
3.1. Nuclear Magnetic Resonance (NMR) Characterization
3.1. Nuclear Magnetic Resonance (NMR) Characterization
NMR enables us to investigate and detect the interactions between the imidazolium ring and its
localNMR enables
vicinity baseduson tothe
investigate
changesand of thedetect the interactions
chemical shifts in thebetween the imidazolium
NMR spectra [47]. The ring and its
magnitude
local vicinityshifts
of chemical basedison the changes
affected by theofsubstitution
the chemicalofshifts in the
a given NMR
atom or spectra [47].group
functional The magnitude
in the given of
chemical
molecule shifts is affected
by another one, andby itthe substitution
strongly depends of on
a given atom or functional
the substituents nature andgroup in the
position given
in respect
molecule by another
to the discussed one, [42].
nucleus and itChen
strongly
et al.depends on the
[47] pointed substituents
out that protons nature
of theand position inring
imidazolium respect
are
to the discussed
notably sensitivenucleus [42]. Chen et al.
to its environmental [47] pointed
changes, whichoutcanthat protons ofinthe
be observed NMR imidazolium
spectra [47].ringPure
are
notably
RILs andsensitive
resultanttoCAP-RILs
its environmental
films werechanges, whichusing
characterized can 1H
be observed in NMR
NMR analysis spectra
in order [47]. Pure
to confirm the
RILs and resultant CAP-RILs films were characterized using 1H NMR analysis
effectiveness of the transesterification reaction between the polymer and studied ionic liquids. in order to confirm
the effectiveness of the
High resolution transesterification
proton reaction
NMR is an excellent between
analytic toolthe polymervarious
to monitor and studied ionicThe
reactions. liquids.
proton
High resolution proton NMR is an excellent analytic tool to monitor various
signal peaks for CAP were as follows: δ 3.2–5.9 ppm (protons of the cellulose backbone, 7H), δ 2.3 ppm reactions. The
proton
(methylsignal peaks
protons for CAP
of acetyl, 3H),were
δ 1.1as
ppmfollows: δ 3.2–5.9
(methyl protonsppm (protons of
of propionyl, theand
3H), cellulose backbone,
δ 2.2 ppm 7H),
(methylene
δprotons
2.3 ppm of(methyl protons
propionyl, of acetyl,
2H) (Figure 3H), δ 1.1 ppm (methyl protons of propionyl, 3H), and δ 2.2 ppm
5A).
(methylene
13C NMR protons of propionyl,
spectrum of pure CAP2H) presents
(Figure 5A).
the shifts δ 170–173 ppm assigned to carbonyl carbons,
whereas the shifts δ 0–30 ppm correspond to the signals of the acyl carbon (Figure 5B). δ 60–110 ppm
correspond to the signals of the anomeric glucose unit (AGU) carbonate region. The peak at 63.0 ppm
is related to the C6 carbon in the acetyl group. The peaks at 78.0 ppm and 101.2 ppm and are assigned
to C4 and C1 in the glucose unit. The observed cluster of resonance peaks of C2, C3, and C5 carbons is
explained by their heavy overlap between 71–74 ppm and associated with high DS sample [48,49].
Polymers 2019, 11, 1217 8 of 23
Polymers 2019, 11, x FOR PEER REVIEW 8 of 23

Figure 5.
5. 1 HH(A)
(A) and1313C (B) NMR spectra of pristine (A1,B1) CAP and RIL1_Br (A2,B2), modified
1
Figure and C (B) NMR spectra of pristine (A1,B1) CAP and RIL1_Br (A2,B2), modified
CAP with 9 wt % of RIL1_Br (A3,B3) and modified CAP with 23 wt % of RIL1_Br (A4,B4).
CAP with 9 wt % of RIL1_Br (A3,B3) and modified CAP with 23 wt % of RIL1_Br (A4,B4).
Polymers 2019, 11, 1217 9 of 23

The presence of RILs influenced the 1H NMR spectra of CAP-RIL films (Figure 5). The peaks of
CAP below 5.5 ppm did not change after the transesterification reaction. It can be seen that the H2
proton at C2 carbon of the imidazole ring is de-shielded, therefore, the H2 proton signal is shifted
for the CAP-RIL films with respect to pure RIL (Table 1), e.g., the chemical shift of the H2 proton in
CAP-9-RIL1_Br from 10.55 to 11.02 ppm in comparison to RIL is observed (Table 1) [50]. Simultaneously,
one of the protons at C4 and C5 carbons in the imidazole ring is shielded and shifted from 7.58 to
7.24 ppm (Figure 5A, Table 1). Shin et al. [51] also noted that only one of the H4, H5 protons shifts
as a result of the change from ethyl to butyl substituent [51]. The aforementioned changes prove the
successful transesterification reaction between the RIL and CAP.

Table 1. The signals position of H2, H4, and H5 protons of the imidazole ring based on NMR spectra of
CAP-RIL1_Br and CAP-RIL2_Br films.

Films Signals Position of a Proton (ppm)

H2 H4 and H5
Pure RIL1_Br 10.55 7.58
CAP-9-RIL1_Br 11.02 7.24
CAP-23-RIL1_Br 11.01 7.21
Pure RIL2_Br 10.17 7.48
CAP-9-RIL2_Br 10.56 7.21
CAP-23-RIL2_Br 10.58 7.24

The quantitative assessment of the transesterification reaction yield between the propanoyloxymethyl
group in CAP and 2-etoxy-2-oxoethyl in RILs was also performed based on the substitution degree
(DS) and discussed from the point of view of RIL content (Table 2, Equation (1)). The occurrence of a
substitution reaction possesses a significant impact on the characteristics of cellulose derivatives, like
crystallinity, solubility, thermal, and mechanical properties [52–54].

Table 2. The degree of substitution (DS) calculated according to 1H NMR spectra for pure RILs and
CAP-RIL films.

Integral of Resonance (-)

Films CAP-9-RIL1_Br CAP-23-RIL1_Br
S1 1.00 (at 7.81 ppm) 1.00 (at 7.82 ppm)
S2 11.43 (at 5.10 ppm) 3.53 (at 5.09 ppm)
DS 0.087 0.283
DSmax 0.099 0.295
Films CAP-9-RIL2_Br CAP-23-RIL2_Br
S1 1.00 (at 7.41 ppm) 1.00 (at 7.24 ppm)
S2 36.88 (at 5.07 ppm) 13.10 (at 5.07 ppm)
DS 0.027 0.076
DSmax 0.076 0.229

DS for the CAP-RIL films was estimated taking into account the ratio of the proton integrals of
the imidazolium ring and AGU according to Equation (1) [37]:

S1
DS = (1)
S2
where, S1 is the integral of the resonance (7.81 ppm) of the imidazolium ring proton, and S2 is the
integral of the resonance (5.10 ppm) of the proton of AGU [52].
Polymers 2019, 11, 1217 10 of 23

The maximum theoretical degree of substitution (DSmax ) was calculated as the ratio of RIL and
anhydroglucose (AGU) molar masses taking into account the weight of RIL and CAP used to prepare
CAP-RIL films according to the following equation (Equation (2)):

MRIL mRIL
DSmax = (2)
MAGU mCAP

where, MAGU is the average molar mass of the AGU unit in CAP (325.67 g mol−1 ), MRIL is the molar
mass of the ionic liquid, and mCAP and mRIL is the weight (g) of CAP and RIL respectively, in a
given CAP-RIL film. MAGU was calculated using the data provided by the producer (Eastman, USA),
concerning the acetyl, propionyl, and free OH groups content in CAP equal to 1.3 wt %, 48.0 wt %,
and 1.7 wt %, respectively. Generally, the primary carbon atom at C6 position (Figure 5A) is the
most reactive CAP substituent. In the case of RIL1_Br possessing two ester groups, it is assumed
that the transesterification reaction takes place only with one ester group due to the steric hindrances.
Therefore, the degree of substitution (DS) and DSmax was calculated taking into account the 1:1 molar
ratio between CAP and RILs.
It can be noticed that the reaction between CAP and RIL led to the various partial substitution
of ester groups in CAP. The calculated degree of substitution was equal to 0.087 and 0.283 for
CAP-9-RIL1_Br and CAP-23-RIL1_Br, as well as 0.027 and 0.076 for CAP-9-RIL2_Br and CAP-23-RIL2_Br,
respectively (Table 2). The comparison of the obtained DS with the DSmax reflects the amount of RIL
that was attached to the polymer chain. For example, the DS = 0.087 for CAP-9-RIL1_Br indicated
that 88% of the ionic liquid was chemically substituted to the CAP. The calculated DS values for
CAP-RIL1_Br films are comparable to the values of the maximum theoretical degree of substitution
that testifies to the high-efficiency of the transesterification reaction between IL and CAP [43]. It was
assumed that the unreacted RIL can form the RIL-reach domains observed by the SEM and AFM
analysis (Figure 7 and Figure S1, respectively). The low value of DS presented in Table 2 can be
explained by the hindrance steric effect as well as by the reactivity of the anion. Heinze et al. [55] as well
as Pinkert and co-workers [12] pointed out that an aldehyde moiety can react with ILs at the reactive
proton in position 2 by the generation a covalent bond between the IL and the aldehyde function from
the cellulose unit [12]. This reaction is predominantly noticeable during the interaction with ionic
liquid containing an imidazolium ring (e.g., 1-ethyl-3-methylimidazolium acetate [55]) and possessing
an acetate group as a counter ion. On the other hand, when a cation is less reactive, e.g., chlorine or
bromide, C-1 peaks (100.3 ppm) of the reducing end groups can still be seen [55] (Figure 5; Figure 6).
This is related to the fact that chloride or bromide containing ionic liquids do not bind so efficiently to
the reducing end of the carbohydrate [12,55]. The results obtained in this work are in accordance with
the abovementioned findings from the scientific literature [12,55]. Although the chemical modification
between polymeric matrix and ionic liquids took place, the effectiveness was not so high. To summarize,
the selected ionic liquids were anchored within the CAP membrane significantly influencing the
material, physicochemical, and transport properties of the formed materials.
Polymers 2019, 11, 1217 11 of 23
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Figure 6.
Figure 6. 11H
H (A)
(A) and 13C
and 13 C(B)
(B)NMR
NMR spectra
spectra of
of pristine
pristine RIL2_Br
RIL2_Br (A1,B1),
(A1,B1), modified
modified CAP
CAP with
with 9 wt %
9 wt % of
of
modified CAP
RIL2_Br (A2,B2) and modified CAP with
with 23
23 wt
wt %
% of
of RIL2_Br
RIL2_Br (A3,B3).
(A3,B3).

3.2. Subsection Conversion

3.2. Subsection Conversion Degree
Degree of
of RIL
RIL
The
The degree
degree ofof RIL
RIL conversion
conversion after
after the
the transesterification
transesterification reaction
reaction with
with CAP
CAP was
was additionally
additionally
examined
examined using
usingthetheLS-MS
LS-MSsystem.
system.The
Theyield
yieldofofthe
thereaction
reactionbetween
between CAP and
CAP RIL
and was
RIL determined
was as
determined
ratios of the difference between calculated peak areas per membrane masses for unreacted
as ratios of the difference between calculated peak areas per membrane masses for unreacted and and studied
membranes versus areas
studied membranes perareas
versus masses
perfor unreacted
masses membranes.
for unreacted Yields amounted
membranes. to 99% and
Yields amounted 91%and
to 99% for
CAP-9-RIL1_Br and CAP-23-RIL1_Br membranes, respectively.
91% for CAP-9-RIL1_Br and CAP-23-RIL1_Br membranes, respectively.

3.3. Morphology of
3.3. Morphology of CAP-RILs
CAP-RILs FilmsFilms
SEM
SEM images
images of of pristine
pristine CAP
CAP and
and CAP
CAP RIL1_Br
RIL1_Br areare presented
presented in in Figure
Figure 7. Results of
7. Results SEM analysis
of SEM analysis
of
of pristine CAP and CAP-based films modified with RILs proved the formation of dense films. The
pristine CAP and CAP-based films modified with RILs proved the formation of dense films. The
morphological study of CAP-RIL films revealed the decreased homogeneity of
morphological study of CAP-RIL films revealed the decreased homogeneity of the film structure with the film structure with
increasing
increasing content
content of of RIL.
RIL. In
In general,
general, atat the
the low RIL content,
low RIL content, the
the film
film surface
surface roughness
roughness is comparable
is comparable
to that of the native CAP, while an increase of RIL content results in the change
to that of the native CAP, while an increase of RIL content results in the change of the film surface, of the film surface,
which
which can evidence the differences in the substitution ability of CAP with RIL. This was reflected by
can evidence the differences in the substitution ability of CAP with RIL. This was reflected by
the
the presence
presence of of RIL-rich
RIL-rich andand CAP-rich
CAP-rich domains
domains on on the
the film
film surface
surface asas well
well as
as by
by the
the appearance
appearance of of
unconnected
unconnected smallsmall pores,
pores, particularly
particularly in in the
the case
case of CAP-RIL2_Br and
of CAP-RIL2_Br CAP-RIL3_BF4 (Figure
and CAP-RIL3_BF4 (Figure 7) 7) films
films
as
as aa result
result of
of the
the increased
increased ionic
ionic liquid
liquid content
content upup to
to 23
23 wt
wt %.
%. InIn the
the case
case of
of RIL1_Br,
RIL1_Br, thethe increase
increase of of
ionic liquid content up to 28 wt % results in the appearance of the IL domains
ionic liquid content up to 28 wt % results in the appearance of the IL domains on the membrane on the membrane surface.
It shouldItbeshould
surface. also remarked that valuesthat
be also remarked of DS (Table
values of 2)
DSfor CAP-9-RIL2_Br
(Table and CAP-23-RIL2_Br
2) for CAP-9-RIL2_Br and CAP-23- are
equal
RIL2_Br to 35% and 33%
are equal respectively,
to 35% thus RIL2_Brthus
and 33% respectively, is not entirelyisbound
RIL2_Br to CAP.
not entirely Therefore,
bound to CAP. theTherefore,
presence
of unbound RIL (RIL-rich domains) can be expected (Figure
the presence of unbound RIL (RIL-rich domains) can be expected (Figure 7). 7).
Polymers 2019, 11, 1217 12 of 23
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Figure
Figure 7.
7. SEM
SEMimages of of
images surface and
surface cross-section
and of (A)
cross-section CAP-RIL1_Br,
of (A) (B) (B)
CAP-RIL1_Br, CAP-RIL2_Br, and and
CAP-RIL2_Br, (C)
CAP_RIL3_BF4 films.
(C) CAP_RIL3_BF4 films.

Taking
Taking into account
account the
the fact
fact that all CAP-based
CAP-based membranes
membranes were were prepared
prepared following
following the
the same
same
procedure,
procedure, the IL IL migration
migrationto tothe
thefilm
filmsurface
surfaceand andthus,
thus,thethe appearance
appearance of of
thethe IL agglomerates
IL agglomerates on
on the
the membrane
membrane surface,
surface, can
can be be enhanced
enhanced by theby the differences
differences in the polymer–RIL
in the polymer–RIL interactions
interactions and RIL and RIL
viscosity.
viscosity. Such was
Such tendency tendency was
noticed bynoticed by de
de los Rios forlos Rios® for
Nylon andNylon ® and Mitex-based
Mitex-based supported
supported liquid liquid
membranes
membranes with 1-butyl-3-methylimidazolium
with 1-butyl-3-methylimidazolium hexafluorophosphate hexafluorophosphate (BMIM)(PF6), 1-butyl-3-
(BMIM)(PF6), 1-butyl-3-methylimidazolium
methylimidazolium tetrafluoroborate
tetrafluoroborate (BMIM)(BF4), (BMIM)(BF4),
and 1-butyl-3-methylimidazolium andbis{(trifluoromethyl)sulfonylimide,
1-butyl-3-methylimidazolium
bis{(trifluoromethyl)sulfonylimide,
(BMIM)(Tf2N) [56]. The researchers observed (BMIM)(Tf2N)the ILs[56]. The researchers
agglomerates with various observed the and
size on Mitex ILs
agglomerates
Nylon membrane with surfaces
various size
as aon Mitex
result of and Nylon membrane
differences surfaces
in ILs viscosity andas a resultThe
fluidity. of differences
procedure in of
ILs viscosityelaboration
membranes and fluidity.
wasThe procedure
identical for allofpolymer-IL
membranes elaboration
systems [56]. Itwas
wasidentical
pointed outfor that
all polymer-IL
the amount
systems [56]. It wason
of IL agglomerated pointed out that the
the membranes amount
surface of IL agglomerated
increases with the rise ofonthe the
ILmembranes surface
viscosity according
increases with the
to the following rise of (BMIM)(PF6)
sequence: the IL viscosity > (BMIM)(BF4)
according to>the following sequence:
(BMIM)(Tf2N) (BMIM)(PF6)
[56]. The researchers >
also
(BMIM)(BF4)
stated that the>homogeneity
(BMIM)(Tf2N) and[56]. The researchers
the good compatibility also stated Nylon
between that the
andhomogeneity
studied ILs wasand correlated
the good
compatibility between Nylon and studied ILs was correlated with their hydrophilic nature in contrast
Polymers 2019, 11, 1217 13 of 23

with their hydrophilic nature in contrast to the hydrophobic Mitex membranes doped with the studied
ionic liquids. The interactions between hydrophilic ILs and Mitex were limited due to the highly
hydrophobic nature of Mitex polymer [56].
Xi et al. [57] indicated that the addition of the high loading of the 1-ethyl-3-methylimidazolium
hexafluorophosphate (EMIM)(PF6) to waterborne polyurethane (WPU) membranes results in the
microphase separation. At high (EMIM)(PF6) content (over 10 wt %) the IL-rich domains were formed
on the membrane surface which was attributed to the incompatibility between the IL and WPU
matrix [57].
The results of the SEM analysis were also evaluated taking into consideration the polymer/ionic
liquid amount ratio used to elaborate a given film. In principle, the transesterification reaction could
theoretically take place between three ester groups in the AGU unit and one ester group in RIL2_Br and
RIL3_BF4 ionic liquids. Therefore, the ratio between CAP and RIL required for the total substitution of
CAP ester by RIL2_Br or RIL3_BF4 is 1 to 3 that would correspond even to the 28.9 wt % of the ionic
liquid in the polymer matrix. The content of ionic liquid in CAP films exceeding this ratio may result
in the release of ionic liquid excess and the formation of RIL-rich domains on the membrane surface.
In fact, RIL-rich agglomerates can be seen for CAP-RIL2 and CAP-RIL3 films containing at least 23
wt % of RIL (Figure 7B,C, respectively). These results suggest that the substitution reaction was not
completed and only two ester groups in AGU could possibly be substituted by RIL2_Br or RIL3_BF4.
Thus, the ratio between the polymer and the ionic liquid is 1:2, which corresponds to around 21 wt %
of the ionic liquid in the polymer matrix. These considerations are in accordance with the results of the
SEM analysis.
Assuming that the transesterification reaction can take place between two ester group in RIL1_Br
and three ester groups in AGU unit, the polymer: RIL1_Br ratio is 2:3, which corresponds to 21 wt % of
RIL1_Br in the polymer matrix. CAP film with the RIL1_Br content equal to 23 wt % does not have
visible changes on the film surface that can confirm the full substitution and the high compatibility
between CAP and RIL1_Br, which is in agreement with a high degree of substitution (Table 1). On the
other hand, in the case of RIL1_Br, the ratio of polymer to RIL1_Br could be 1:3, taking into account
the steric hindrance that might result from the branched structure of the ionic liquid. The further
increase of RIL1_Br content up to 28 wt % led to the change of the membrane surface and appearance
of heterogeneity on its surface (Figure 7).
Figure 8 presents the SEM-EDX mapping of native CAP and modified CAP-based films. In the
EDX images of pristine CAP film, the characteristic elements assigned as carbon and oxygen can be
observed. The presence of carbon and oxygen results from the chemical composition of the polymer.
The new signal of bromine was detected by EDX analysis for CAP-RIL1_Br and CAP-RIL2_Br. In the
case of CAP-RIL2_Br films containing 23 wt % and 28.6 wt % of ionic liquid, the RIL-rich domain on
the film surface was also observed (Figure 8B). In the case of CAP-RIL_BF4, the boron atom cannot be
detected due to the limitation of SEM-EDX analysis, therefore, the mapping for CAP-RIL_BF4 films
was not shown. SEM-EDX is more suitable for heavy atoms analysis, therefore the light atoms such as
boron are not detected, or they give false signals. The comparable results related to the monitoring of
ILs behavior after modification with the polymeric matrix were presented by de los Rios et al. [56]. The
authors observed that the studied imidazolium-based ionic liquids are homogeneously distributed
within Nylon® membranes which was reflected by the SEM-EDX analysis recorded at the membrane
cross-section [56]. Xi et al. [57] reported the homogenous dispersion of 1-ethyl-3-methylimidazolium
hexafluorophosphate (EMIM)(PF6) in the waterborne polyurethane (WPU) membranes up to the 10 wt
% of (EMIM)(PF6). The increase of the (EMIM)(PF6) content above 10 wt % resulted in the formation of
IL-rich domains that were dispersed in the WPU matrix [57].
 Polymers 2019, 11, 1217 14 of 23
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SEM-energy
Figure8.8.SEM-
Figure energydispersive
dispersiveX-ray
X-ray(EDX)
(EDX)images
imagesofoffilm
filmsurface:
surface:(A)
(A)CAP
CAPand
andCAP-RIL1_Br
CAP-RIL1_Brand
and
(B) CAP and CAP-RIL2_Br films (green—carbon atoms, red—bromine atoms, and blue—oxygen
(B) CAP and CAP-RIL2_Br films (green—carbon atoms, red—bromine atoms, and blue—oxygen atoms).
atoms).
The film surface morphology was also studied and visualized by using AFM analysis and discussed
based
Theonfilm
the roughness average parameter
surface morphology was also(Ra) studied(FigureandS1). The performed
visualized by using AFM AFM analysis
analysisrevealed
and
that the addition of RIL influences the surface roughness of tested films
discussed based on the roughness average parameter (Ra) (Figure S1). The performed AFM analysis (Figure S1). The increase of the
surface roughness of CAP-RIL films with the rise of the RIL content was
revealed that the addition of RIL influences the surface roughness of tested films (Figure S1). The observed. Such an effect was
the mostofpronounced
increase the surface in the case of
roughness of RIL3_BF4
CAP-RIL incorporation
films with thetorise theoffilm
thematrix. Therefore,
RIL content only these
was observed.
results
Such an are shown
effect was the in Figure S1. Three-dimensional
most pronounced in the case (3D) images of
of RIL3_BF4 CAP-RIL3_BF4
incorporation films
to the filmreflect the
matrix.
increase of the surface roughness. This result is related to the appearance
Therefore, only these results are shown in Figure S1. Three-dimensional (3D) images of CAP- of the RIL-rich domains on
the CAP-based
RIL3_BF4 film surface,
films reflect which is
the increase ofinthe
accordance with the results
surface roughness. obtained
This result by SEMto(Figure
is related 7) analysis.
the appearance
In the case of the sample containing the highest level of IL, i.e., CAP-23-RIL3_BF4,
of the RIL-rich domains on the CAP-based film surface, which is in accordance with the results the hills in the x
direction were observed. It was related to the lower viscosity of the RIL3_BF4
obtained by SEM (Figure 7) analysis. In the case of the sample containing the highest level of IL, i.e., IL in the comparison
to polymeric matrix
CAP-23-RIL3_BF4, theand
hillshigher
in theinteraction
x direction between IL and AFM
were observed. It wasprobe.
relatedXitoettheal.lower
[57] applied
viscosity AFMof
analysis and observed an increase of the surface roughness of the
the RIL3_BF4 IL in the comparison to polymeric matrix and higher interaction between IL and AFMwaterborne polyurethane (WPU)
membranes
probe. with
Xi et al. [57]increasing
applied AFM IL content.
analysisItand wasobserved
found that anthe presence
increase of (EMIM)(PF6)
of the surface roughness disrupts the
of the
polymer chains
waterborne order resulting
polyurethane (WPU)in membranes
the rougher with WPU-(EMIM)(PF6) membranes
increasing IL content. compared
It was found to thethe
that flat
surface of pristine WPU. For example, the value of Ra parameter
presence of (EMIM)(PF6) disrupts the polymer chains order resulting in the rougher WPU- increased from 0.81 nm for pure
WPU up to 6.89
(EMIM)(PF6) nm for WPU
membranes comparedmembraneto the with 15 wt %
flat surface of of (EMIM)(PF6)
pristine WPU. For [57]. Moreover,
example, the authors
the value of Ra
highlighted that ILs appeared on the surface of the polymeric
parameter increased from 0.81 nm for pure WPU up to 6.89 nm for WPU membrane with 15 wt %membranes and generated thin films
of
(EMIM)(PF6) [57]. Moreover, the authors highlighted that ILs appeared on the surface of theIL
due to the low viscosity of the used ILs. The researchers also found that the incorporation of high
content leads
polymeric to the phase
membranes andseparation
generatedand thinthus,
filmsthe due
occurrence
to the of lowtheviscosity
IL-rich domains of (EMIM)(PF6)
of the used ILs. The
precipitated on the membrane surface [57].
researchers also found that the incorporation of high IL content leads to the phase separation and
thus, the occurrence of the IL-rich domains of (EMIM)(PF6) precipitated on the membrane surface
3.4. Thermogravimetric (TGA) Analysis
[57].
Figure 9 presents thermogravimetric (TGA) and derivative thermogravimetric (DTG) curves for
3.4.
theThermogravimetric
pristine CAP, pure(TGA)
RILs, Analysis
and CAP-RIL films. The degradation of pure CAP films takes place in one
stage, and it corresponds to the simultaneous loss of acetyl and propionyl groups from the cellulose
Figure 9 presents thermogravimetric (TGA) and derivative thermogravimetric (DTG) curves for
backbone and the pyrolysis of cellulose structure which occurs in the temperature range 300–420 ◦ C.
the pristine CAP, pure RILs, and CAP-RIL films. The degradation of pure CAP films takes place in
In the case of pure RIL1_Br, RIL2_Br, and RIL3_BF4 numerous decomposition stages can be observed
one stage, and it corresponds to the simultaneous loss of acetyl and propionyl groups from the
(Figure 9A2–C2).
cellulose backbone and the pyrolysis of cellulose structure which occurs in the temperature range
300–420 °C. In the case of pure RIL1_Br, RIL2_Br, and RIL3_BF4 numerous decomposition stages can
be observed (Figure 9A2–C2).
Polymers 2019, 11, 1217 15 of 23

Polymers 2019, 11, x FOR PEER REVIEW 15 of 23

Figure 9. Thermogravimetric analysis of CAP-RIL films. A1, B1, C1-TGA and A2, B2, C2-DTG curves.
Figure 9. Thermogravimetric analysis of CAP-RIL films. A1, B1, C1-TGA and A2, B2, C2-DTG curves.

TGA
TGA analysis
analysis of of pure ionic liquids
pure ionic liquids revealed
revealed the presence of
the presence moisture, indicated
of moisture, indicated by by the
the peak
peak at
at
around
around 100
100 °C.
◦ C. These
These observations
observations were
were supported
supported and and proved
proved by by the
the infrared
infrared spectra
spectra (Figure
(Figure 9).
9).
The presence
The presence of
of moisture
moisture was was referred
referred to
to by
bythe
thepeaks
peaksobserved
observedatatca.
ca.3390
3390cm
−1. The highest level of
cm−1 . The highest level
moisture hashas
of moisture been
beendetected for for
detected RIL1_Br andand
RIL1_Br slightly smaller
slightly for RIL2_Br.
smaller On the
for RIL2_Br. Onother hand,hand,
the other no such
no
observation was found
such observation for RIL3_BF4
was found ILs both
for RIL3_BF4 ILson the on
both TGA-DTG (Figure(Figure
the TGA-DTG 9C1,C2)9C1,C2)
and infrared spectra
and infrared
(Figure 10). The
spectra (Figure 10).absorbed moisture
The absorbed by the
moisture by RIL1_Br
the RIL1_Br andandRIL2_BF4
RIL2_BF4waswasrelated
relatedtototheir high
their high
hygroscopic properties. The degradation stage between 190–280◦ °C corresponds to the
hygroscopic properties. The degradation stage between 190–280 C corresponds to the decomposition of decomposition
of imidazolium
imidazolium sideside chains
chains [58,59].
[58,59]. Erdmenger
Erdmenger et al.etsuggested
al. suggested thatdegradation
that the the degradation of imidazolium-
of imidazolium-based
based ionic liquid containing tetrafluoroborate anion leads to the creation of alkylimidazole, alkyl
fluoride and BF3 [60]. RIL2_Br possesses similar thermogram to RIL3_BF4, whereas RIL1_Br
decomposition starts at lower temperature values compared to RIL2_Br and RIL3_BF4. In Figure
Polymers 2019, 11, 1217 16 of 23

ionic liquid containing tetrafluoroborate anion leads to the creation of alkylimidazole, alkyl fluoride
and BF3 [60]. RIL2_Br possesses similar thermogram to RIL3_BF4, whereas RIL1_Br decomposition
Polymers 2019, 11, x FOR PEER REVIEW 16 of 23
starts at lower temperature values compared to RIL2_Br and RIL3_BF4. In Figure 10A1–C1 it can be
seen that RIL3_BF4
10A1–C1 possesses
it can be seen a higher temperature
that RIL3_BF4 possesses a of degradation
higher compared
temperature to RIL1_Brcompared
of degradation and RIL2_Br.
to
This difference is mainly related to the less branched structure of RIL1_Br and RIL2_Br imidazolium
RIL1_Br and RIL2_Br. This difference is mainly related to the less branched structure of RIL1_Br and
cation (Figure
RIL2_Br 2).
imidazolium cation (Figure 2).

Figure
Figure 10.
10. Infrared
Infrared spectra
spectra for
for pure
pure ionic
ionic liquids.
liquids.

Raj et al. [61] suggested

Raj suggested that that the
the nature of the anions influences the thermal stability stability of
of an ionic
liquid. Cao
liquid. Caoet et al.
al. [62]
[62] observed
observed that that strongly
strongly coordinating
coordinating anions,
anions, such
such as as halogen
halogen (Cl–,
(Cl–, Br–
Br– or
or I–),
I–),
decrease the IL degradation temperature, whereas anions which are
decrease the IL degradation temperature, whereas anions which are weakly coordinated (e.g., BF4–,weakly coordinated (e.g., BF4–,
PF6–) will
PF6–) will lead
lead to a higher IL decomposition temperature. The The obtained
obtained results
results for
for CAP-RIL
CAP-RIL films
revealed the
revealed the drop
dropofoffilm filmthermal
thermalstability
stability in in
comparison
comparison to pure CAP
to pure duedue
CAP to theto incorporation of ionic
the incorporation of
liquid, which is in accordance with the results found by Rynkowska et
ionic liquid, which is in accordance with the results found by Rynkowska et al. [19] for CAP-based al. [19] for CAP-based firms
containing
firms 1-methyl-3-(4-vinylbenzyl)-1H-imidazole-3-ium
containing 1-methyl-3-(4-vinylbenzyl)-1H-imidazole-3-ium chloridechloride
polymerizable ionic liquid.
polymerizable In
ionic
the Figure
liquid. 9A2–C2
In the Figure it can beitalso
9A2–C2 cannoticed that thethat
be also noticed peaktheintensity at around
peak intensity 370 ◦ C370
at around diminished with
°C diminished
increasing
with content
increasing of RIL
content ofinRIL
theinfilmthematrix and the
film matrix and peak
the position shifts shifts
peak position to lower temperature
to lower value.
temperature
Moreover, the increase in peak in intensity at around ◦ C was found due to the increasing content of
value. Moreover, the increase peak intensity at 290
around 290 °C was found due to the increasing
RIL in the
content of film
RIL matrix.
in the film Thematrix.
highestThe increase
highest of this degradation
increase peak simultaneously
of this degradation with the reduction
peak simultaneously with
of the degradation ◦
the reduction of thepeak at 370 C peak
degradation was observed
at 370 °Cin theobserved
was case of CAP films
in the casewith the 28.6
of CAP wt with
films % of RIL2_Br
the 28.6
and%RIL3_BF4
wt of RIL2_Br (Figure 9B2,C2, respectively).
and RIL3_BF4 (Figure 9B2,C2, Such behavior is related
respectively). to the presence
Such behavior is relatedof to
thethe
unbounded
presence
RIL, which was revealed by SEM and SEM-EDX analysis (Figure
of the unbounded RIL, which was revealed by SEM and SEM-EDX analysis (Figure 7; Figure 8, 7; Figure 8, respectively).
It was found that the maximum degradation temperature (Tmax ) at the first degradation peak of
respectively).
CAP-RIL1_Br membranes ◦ C. Whereas in the case of CAP-RIL2_Br and CAP-RIL3_BF4 it
It was found that the is around 150
maximum degradation temperature (Tmax) at the first degradation peak of
◦
is equal to 200membranes
C (Figure 9). Hence,150 the°C.membranes thermal stability is found toand be CAP-RIL3_BF4
satisfactory for
CAP-RIL1_Br is around Whereas in the case of CAP-RIL2_Br
their
it potential
is equal to 200further
°C (Figureapplication
9). Hence, in the
thepervaporation
membranes thermal or gasstability
separation processes,
is found to be carried out at
satisfactory fora
temperature usually up to 110 ◦ C.
their potential further application in the pervaporation or gas separation processes, carried out at a
temperature usually up to 110 °C.
3.5. Membrane Surface Hydrophilicity
3.5. Membrane Surface Hydrophilicity
In the formation of a new type of materials, an important part of research is related to their
physiochemical properties.
In the formation of a new In type
the presented work,
of materials, an water contact
important partangle (WCA)isand
of research surface
related free
to their
energy (SFE) with
physiochemical partial components
properties. (e.g., polar
In the presented andwater
work, dispersive parts)
contact were
angle determined
(WCA) (Figurefree
and surface 11).
energy (SFE) with partial components (e.g., polar and dispersive parts) were determined (Figure 11).
The surface free energy was calculated based on the Owens, Wendt, Rabel, and Kaelble (OWRK)
method [63]. In the case of all functionalized membranes with ILs, the presence and amount of ionic
liquid has a significant impact on the material properties. Due to the differences in hydrophilicity of
the ionic liquids, the substantial influence on contact angle values was observed (Figure 11A–C). In
 Polymers 2019, 11, x FOR PEER REVIEW 17 of 23

Polymers 2019, 11, 1217 17 of 23

all cases, with the increasing amount of ILs in the polymeric matrix, a reduction of WCA has been
found. For the pristine CAP material, the contact angle value was equal to 84.3 ± 3.1°. However, the
strongest
The surfaceeffect
free was
energyfound
wasin calculated
the case of based
CAP-based membranes
on the containing
Owens, Wendt, RIL3_BF4
Rabel, ionic liquid,
and Kaelble (OWRK)
WCA CAP_28.6_RIL3_BF4 = 55.7 ± 2.1° (Figure 11C).
method [63]. In the case of all functionalized membranes with ILs, the presence and amount of ionic
liquidForhasthe membranesimpact
a significant modified onwith
the RIL1_Br
materialand RIL2_Br the
properties. Duecontact
to theangle values for
differences in the samples
hydrophilicity
containing 28.6 wt % of RIL were equal to 71.3° ± 2.0° and 74.6° ± 3.0°, respectively (Figure 11A,B).
of the ionic liquids, the substantial influence on contact angle values was observed (Figure 11A–C).
The obtained data revealed the efficiency of the polymeric membranes modification from the point
In all cases, with the increasing amount of ILs in the polymeric matrix, a reduction of WCA has been
of view of material properties. Taking into account surface free energy, an important◦ impact was
found. For the pristine CAP material, the contact angle value was equal to 84.3 ± 3.1 . However, the
noticed for the polar part of the overall SFE (Figure 11D–F). This observation was related to the fact
strongest effect was found in the case of CAP-based membranes containing RIL3_BF4 ionic liquid,
that hydrophilicity influences polar interaction the most. An addition of hydrophilic ILs to the
WCA CAP_28.6_RIL3_BF4
polymeric = 55.7 the
matrix influenced ± 2.1 ◦ (Figure 11C).
dispersive part of SFE to a much less extent (Figure 11).

Figure11.
Figure 11. Physiochemical
Physiochemicalcharacterization of the
characterization formed
of the polymeric
formed materials
polymeric modified
materials with ILs.
modified A– ILs.
with
C—water contact angle, D–F—surface free energy.
A–C—water contact angle, D–F—surface free energy.

3.6. For
Mechanical Propertiesmodified with RIL1_Br and RIL2_Br the contact angle values for the samples
the membranes
containing 28.6 wt % ◦ ± 2.0◦ and 74.6◦ ± 3.0◦ , respectively (Figure 11A,B).
The influence ofof RILincorporation
RILs were equal tointo 71.3the polymer matrix on the mechanical properties of
The obtainedfilms
CAP-based data was
revealed
also the efficiencyby
investigated of tensile
the polymeric
tests andmembranes modification
was evaluated in terms from the point
of Young’s
ofmodulus
view of(E),
material properties.
stress at break (σmaxTaking into account
), and elongation surface
at break (εmaxfree energy, an important impact was
) parameters.
noticed forpristine
The the polar partfilm
CAP of the overall which
is brittle, SFE (Figure 11D–F).
is reflected byThis observation
Young’s wasstress
modulus, related to the fact
at break, andthat
elongation at break
hydrophilicity values
influences equal
polar to E = 1,220
interaction the ±most.
63 MPa, σmax = 49of
An addition ± hydrophilic
3 MPa, and ILs
εmax to
= the
53%polymeric
± 5%,
respectively
matrix (Figure
influenced the12). The comparison
dispersive of the
part of SFE toresults
a much forless
CAP-based membranes
extent (Figure 11). with the pure CAP
revealed the significant change of the mechanical properties as a result of the RILs incorporation. It
3.6.
wasMechanical Properties
observed that the increasing RIL content enhances the elasticity and simultaneously reduces the
brittleness of CAP-based materials (Figure 12), which is reflected by the increasing elongation at
The influence of RILs incorporation into the polymer matrix on the mechanical properties of
break value and decreasing values of stress at break and elastic modulus. The elastic modulus value
CAP-based films was also investigated by tensile tests and was evaluated in terms of Young’s modulus
decreased from 1220 MPa for pure CAP to around 600 MPa for CAP-RIL membranes containing 28.6
(E), stress at break (σmax ), and elongation at break (εmax ) parameters.
wt % of RIL. Simultaneously, the elongation at break value increased from 53% for pure CAP to
The pristine CAP film is brittle, which is reflected by Young’s modulus, stress at break, and
around 85% for CAP-RIL films containing 28.6 wt % of RIL. The decrease of stress at break values as
elongation at break values equal to E = 1,220 ± 63 MPa, σmax = 49 ± 3 MPa, and εmax = 53% ± 5%,
respectively (Figure 12). The comparison of the results for CAP-based membranes with the pure CAP
revealed the significant change of the mechanical properties as a result of the RILs incorporation.
Polymers 2019, 11, 1217 18 of 23

It was observed that the increasing RIL content enhances the elasticity and simultaneously reduces
the brittleness of CAP-based materials (Figure 12), which is reflected by the increasing elongation
at break value and decreasing values of stress at break and elastic modulus. The elastic modulus
value decreased from 1220 MPa for pure CAP to around 600 MPa for CAP-RIL membranes containing
28.6 wt % of RIL. Simultaneously, the elongation at break value increased from 53% for pure
Polymers 2019, 11, x FOR PEER REVIEW
CAP to
18 of 23
around 85% for CAP-RIL films containing 28.6 wt % of RIL. The decrease of stress at break values as a
function
a functionof RIL
of RILcontent cancan
content be be
seen from
seen 49 49
from to around
to around25 25
MPa forfor
MPa pure CAP
pure CAPand CAP-28.6-RIL
and CAP-28.6-RIL films,
respectively. Such behavior
films, respectively. corresponds
Such behavior to the reduced
corresponds to the rigidity
reducedofrigidity
CAP-based films withfilms
of CAP-based simultaneous
with
improvement
simultaneous of their elongation.
improvement The
of their obtained results
elongation. of the studied
The obtained mechanical
results of the studiedproperties
mechanical of the
properties
CAP-RIL of the
films CAP-RIL
testifies the films testifies the
plasticization of plasticization
CAP membrane of CAP membrane
materials materials by RIL.
by RIL.

Figure 12.
Figure 12. Young’s
Young’s modulus
modulus(A),
(A),stress
stressatatbreak
break(B),
(B),and elongation
and at break
elongation (C)(C)
at break of the CAP-based
of the CAP-based
membranes modified
membranes modified with
with RILs.
RILs.

The plasticization
The plasticization phenomena
phenomenaofofpolymer
polymermembranes
membranes byby ionic liquid
ionic were
liquid alsoalso
were observed by by
observed
Schmidtetetal.
Schmidt al.[64].
[64]. The
The authors
authors found that the incorporation
incorporation ofof imidazolium-based
imidazolium-basedionic ionicliquids
liquidsled
led to
to the plasticization of ®
Nafion ® 117 matrix. This fact was confirmed by the diminished Young’s
the plasticization of Nafion 117 matrix. This fact was confirmed by the diminished Young’s modulus
modulus
value value compared
compared to theNafion
to the pristine ® Nafion
pristine ® 117 membrane [64], and it was explained by the
117 membrane [64], and it was explained by the presence
ofpresence of the
the butyl andbutyl
hexyl and hexyl
alkyl alkyl
side side chains
chains in theinused
the used
ionicionic
liquid.liquid. It was
It was alsopointed
also pointedoutout that
that the
the incorporation of ionic liquids with side chains characterized by high flexibility weakens
incorporation of ionic liquids with side chains characterized by high flexibility weakens the hydrogen the
hydrogen bonds between sulfonic groups in the Nafion membrane [64]. The similar phenomenon of
bonds between sulfonic groups in the Nafion membrane [64]. The similar phenomenon of polymer
polymer membrane plasticization by ionic liquid incorporation was reported by Chen et al. [65] for
membrane plasticization by ionic liquid incorporation was reported by Chen et al. [65] for sulfonated
sulfonated poly(ether ether ketone) (SPEEK) membranes doped with 1-ethyl-3-methylimidazole
poly(ether ether ketone) (SPEEK) membranes doped with 1-ethyl-3-methylimidazole tetrafluoroborate
tetrafluoroborate or 1-butyl-3-methylimidazole methanesulfonate ionic liquids.
or 1-butyl-3-methylimidazole methanesulfonate ionic liquids.
3.7. Transport Properties
3.7. Transport Properties
Taking into account the application of the prepared materials, it is essential to characterize not
Taking into account the application of the prepared materials, it is essential to characterize not
only their mechanical stability but also their transport features. The transport properties of the pure
only their mechanical stability but also their transport features. The transport properties of the pure
CAP and CAP containing RILs were studied by permeation tests with liquid water. Taking into
CAP and kinetics
account CAP containing
of water RILs were studied
permeation, by permeation
the experimental tests
curves ofwith
waterliquid water.fitted
flux were Taking into account
considering
kinetics of water permeation, the experimental curves of water flux were fitted
the possible water plasticization effect in CAP-based membranes in the function of local considering thewater
possible
water plasticization
concentration C based effect in CAP-based
on Equation (3) [66].membranes in the function of local water concentration C
based on Equation (3) [66].
DD==DD0eeγC (3)
(3)
where, D0 is the diffusion coefficient when water concentration tends to have the value equal to 0, γ
where, D0 is the diffusion coefficient when water concentration tends to have the value equal to 0, γ is
is the plasticization factor, and C is the local water concentration in the material [66].
the plasticization factor, and C is the local water concentration in the material [66].
In the Figure 13A–D, the curves for water flux in a dimensionless scale of flux and time are
In the Figure 13A–D, the curves for water flux in a dimensionless scale of flux and time are
presented for pristine polymeric material (Figure 13A) and modified membranes containing 9 wt %
presented
of all typesforofpristine polymericionic
the investigated material (Figure
liquids 13A)
(Figure and modified
13B–D). membranes
In all cases, very goodcontaining 9 wt %
fitting of the
ofexperimental
all types ofdata
the investigated ionic
to the simulated liquids
values has (Figure 13B–D).
been found In allfluxes
for water cases,ofvery good materials.
CAP-RILs fitting of the
The determined values of permeability for water were gathered and presented in Figure 13E. It was
noticed that the presence and, more importantly, the amount of ionic liquid, influenced the transport
properties. The reduction of water barrier properties was observed with the increasing value of RIL.
On the other hand, the type of ionic liquid has no important impact on the permeability. The most
permeable material was the CAP modified with RIL2_Br (Figure 13E). This phenomenon can be
Polymers 2019, 11, 1217 19 of 23

experimental data to the simulated values has been found for water fluxes of CAP-RILs materials.
The determined values of permeability for water were gathered and presented in Figure 13E. It was
noticed that the presence and, more importantly, the amount of ionic liquid, influenced the transport
properties. The reduction of water barrier properties was observed with the increasing value of RIL.
On the other hand, the type of ionic liquid has no important impact on the permeability. The most
permeable material was the CAP modified with RIL2_Br (Figure 13E). This phenomenon can be related
Polymers 2019, 11, x FOR PEER REVIEW 19 of 23
to the fact that IL possessing one reactive group was modified with a much higher effectiveness due
to therelated
lack oftohindrance
the fact thatstericILeffects. The one
possessing lowest transport
reactive group behavior was observed
was modified for thehigher
with a much polymeric
samples with RIL3_BF4
effectiveness due to the addition. In that case,
lack of hindrance the variations
steric effects. The lowestaretransport
associated with was
behavior the observed
presence of a
for the
counter ionpolymeric samples
with different with RIL3_BF4
chemistry addition. In that The
and hydrophobicity. case,more
the variations
profound areinfluence
associatedwas
withobserved
the
presence of a counter ion with different chemistry and hydrophobicity. The more profound
for the samples containing higher levels of ionic liquid, i.e., 16.7 wt %. Based on the literature, the influence
was observed
polymeric for the
films, e.g., samples containing
polystyrene higher levels
(which adsorb of ionic
only little liquid, of
amount i.e.,water),
16.7 wtbehave
%. Basedaton
low thevapor
literature, the polymeric films, e.g., polystyrene (which adsorb only little amount of water), behave
pressures in the accordance with Fick’s law, and permeation velocity is inversely proportional to film
at low vapor pressures in the accordance with Fick’s law, and permeation velocity is inversely
thickness. For higher pressures where increased sorption of water takes place, deviations from Fick’s
proportional to film thickness. For higher pressures where increased sorption of water takes place,
law were observed
deviations from [67,68].
Fick’s law were observed [67,68].

Figure
Figure 13. 13. Transportproperties
Transport properties ofof pristine
pristineand modified
and materials,
modified A–D curves
materials, of experimental
A–D curves and
of experimental
simulated water
and simulated waterflux
fluxforfor
investigated
investigatedmaterials (A-CAP,
materials B-CAP-9-RIL1_Br,
(A-CAP, C-CAP-9-RIL2_Br,
B-CAP-9-RIL1_Br, D-
C-CAP-9-RIL2_Br,
CAP-9-RIL3_BF4) and water permeability as the function of ILs content (E). Barrer is equal to 3.35 x
D-CAP-9-RIL3_BF4) and water permeability as the function of ILs content (E). Barrer is equal to
10−16 mol m m−2 s−1 Pa−1 in SI unit.
3.35 × 10−16 mol m m−2 s−1 Pa−1 in SI unit.
4. Conclusions
In the presented work, the efficient method based on the transesterification reaction for the
chemical modification of CAP-based films with various ester-functionalized imidazolium-based
reactive ionic liquids (RILs) has been developed. Ionic liquids were synthesized and their structures
were identified by NMR spectra. It was found that the molecular structure of RILs possesses the
Polymers 2019, 11, 1217 20 of 23

4. Conclusions
In the presented work, the efficient method based on the transesterification reaction for the chemical
modification of CAP-based films with various ester-functionalized imidazolium-based reactive ionic
liquids (RILs) has been developed. Ionic liquids were synthesized and their structures were identified
by NMR spectra. It was found that the molecular structure of RILs possesses the predominant effect on
the prepared CAP-based films. The conversion degree of RIL in the transesterification reaction was in
the range 88%–96% for RIL1_Br ionic liquid, however it was much lower for RIL2_Br (ca. 35%). This
low value of conversion degree results mainly from the hindrance steric effects. Unreacted ionic liquid
formed RIL-reach domains observed clearly using AFM and SEM analyses. The ionic liquids with a
less branched imidazolium-based cation as well as with the weaker coordination and less hydrophilic
anion provided the superior thermal stability of CAP-based film materials. Water permeation transport
properties of the fabricated materials were determined and referred to RILs structure. It was found
that type of the ionic liquids (type of anion) as well as the amount of the ILs in the polymeric matrix
has a direct impact on the transport properties.

Supplementary Materials: The following are available online at http://www.mdpi.com/2073-4360/11/7/1217/s1,

Figure S1. AFM analysis (3D profile) of pristine CAP pure and CAP-RIL3_BF4 films.
Author Contributions: Conceptualization, W.K. and K.F.; methodology, E.R., K.D., W.K., K.F., and A.W.; validation,
E.R., K.D., J.K., K.F., and A.W.; investigation, E.R., K.D., K.F., and J.K.; data curation, E.R., K.F., J.K., W.K., and
A.W.; writing—original draft preparation, E.R., K.K., J.K., K.F., and K.D.; writing—review and editing, W.K., J.K.,
K.F., and G.L.; visualization, E.R., K.K., and J.K.; supervision, W.K. and K.F.; project administration, W.K. and K.F.;
funding acquisition, W.K. and K.F.
Funding: This project received funding from the Polish National Science Centre (project 2015/18/M/ST5/00635)
and was supported by Hubert Curien’s Partnership Program “Polonium” (35501/2016). Edyta Rynkowska
acknowledges the financial support of the French Government and the French Embassy in Poland (scholarships
848642E, 878205J, 912422E).
Conflicts of Interest: The authors declare no conflict of interest.

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