Cellulosic poly(ionic liquid)s: Synthesis, characterization and application in the cycloaddition of CO2 to epoxides

Article abstract of DOI:10.1039/c5ra05667e

Cellulosic poly(ionic liquid)s (PILs) were prepared via nucleophilic substitution of chlorinated cellulose by 1-methyl-imidazole and their structure and thermal properties have been fully characterized; the cellulosic PILs were found to be green, efficien

Full text of DOI:10.1039/c5ra05667e

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DOI: 10.1039/C5RA05667E
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Cellulosic Poly(ionic liquid)s: Synthesis, Characterization and its
Application in the cycloaddition of CO to Epoxides†
2
Received 00th January 20xx,
Accepted 00th January 20xx
a,b
a
a
a
b
Qin Chen, Chang Peng, Haibo Xie,* Zongbao kent Zhao* and Ming Bao
DOI: 10.1039/x0xx00000x
www.rsc.org/
Cellulosic poly(ionic liquid)s (PILs) were prepared via nucleophilic advantages of natural abundance, low cost, nontoxicity,
20
substitution of chlorinated cellulose by 1-methyl-imidazole and biocompatibility and biodegradability . The preparation of
their structure and thermal properties have been fully biopolymers-based PILs is mainly depended on the chemical
characterized; the cellulosic PILs were found as green, efficient reactions of its hydroxyl groups. For example, the cellulose-
and recyclable catalysts for the cycloaddition of CO to epoxides based PILs (quaternized cellulose) have been synthesized via
2
under solvent-free conditions.
etherification reaction and widely used in various fields for a
long time, such as environmental protection, water treatment,
17, 21
22
Ionic liquids (ILs) are molten salts at relatively low
temperatures and exhibit a series of unique properties
comparing with molecular solvents and materials, which make
them interesting as new solvents, catalysts and functional
textile dyeing industry
etherification reagents,
trimethylammonium chloride (CHTAC) has been the most
and gene transfection . Among the
the 3-chloro-2-hydroxypropyl
22-24
preferred one
. The etherification reaction is usually
1-3
materials . The introduction of ILs moiety into polymers
results in a new family of polymeric materials, poly(ionic
liquid)s (PILs), with particular properties and interesting
carried out under aqueous alkaline conditions, and excess
amount of sodium hydroxide is usually required to achieve
satisfactory modification efficiency. Additionally, the
etherification protocol also suffers from drawbacks such as
side reaction, low modification efficiency, and low structural
4-7
applications . For example, considering the catalytic
performance of ionic liquids moiety, PILs could be used as
efficient heterogeneous catalysts with enhanced recyclability,
25, 26
diversity
. Another choice of biopolymer as a backbone of
such as cyclic addiction of epoxides with CO to prepare cyclic
2
PILs is chitosan due to its active functional groups, including
hydroxyl groups and amino groups. For example, chitosan-
based PILs have been prepared via a direct alkylation of amino
8
-10
carbonates
.
Up to now great efforts have been devoted to synthesize
PILs and two distinctive strategies have been developed: (1)
polymerization of polymerizable ILs monomers, (2) post-
27-29
group, which were successfully used in green catalysis
. He
L. N. et al. prepared chitosan supported PILs via the reaction
5
30
modification of existing polymers . Generally, the
between chitosan and CHTAC. Park D. W. proposed another
method in which the quaternization is occurred on the primary
1
1, 12
polymerizable ILs monomers containing (meth)acryloyl
,
13
14
styrenic or vinyl groups can be employed to synthesize PILs
via traditional polymerization technologies. PILs with special
polymeric backbones can be achieved by post-modification of
amine on chitosan rather than anchoring
a
prebuilt
31, 32
quaternized group onto chitosan.
. Dupont et al.
demonstrated that imidazolium-based ILs were great
candidates for the formation and stabilization of metal
1
5-17
either of synthetic polymers or biopolymers
chloromethyl is introduced onto the synthetic polymers firstly,
followed by an alkylation of Lewis organic bases and anion
. Usually, a
3
, 33, 34
nanoparticles.
Thereby it is still incentive to develop
more facile route to prepare cellulosic PILs, especially with the
imidazolium group
1
8, 19
exchange reaction to obtain the designable PILs
.
Compared with those synthetic polymers, the use of
biopolymers as backbone of PILs is anticipated to provide
a.
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian
1
16023, PR China.
b.
Dalian National Laboratory for Clean Energy; Dalian Institute of Chemical Physics,
CAS, Dalian 116023, PR China; E-mail: hbxie@dicp.ac.cn, zhaozb@dicp.ac.cn
Electronic Supplementary Information (ESI) available: Experimental details and
†
some characterization of cellulosic PILs. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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A: The common protocol for the sysnthesis of imidazolium ionic liquids
o
and 100 C, respectively (Table 1, entries 5, 6), which were
lower than those obtained under neat conditions (Table 1,
View Article Online
DOI: 10.1039/C5RA05667E
CH3
R
CH3 Anion exchange
X
N
N
+
RX
N
N
Imidazolium ionic liquids with
varous anions
X=Cl, Br, I
R= alkyl
entries 2, 3). The results suggest that the use of DMSO as
solvent cannot promote the alkylation reaction, but can
suppress the degradation of CDC. In the case of AmimCl, the
reaction was performed under homogeneous condition as the
ionic liquids were good solvents to CDC; surprisingly, the
product with lower DS of 0.3 was obtained, which were similar
Imidazolium ionic liquids precusor
B: The new protocol for the preparation of cellulosic PILs precusor by chlorinated cellulose
OH
R
CH3
N
N
R
O
DMF SOCl2
O
O
HO
O
0 o
HO
O
O
8
C
OH
n
OH
HO
n
OH
CH3
Cl
n
R=OH or Cl
DS=0.89
N
R=OH, Cl or
N
35
to the amination of cellulose . It seems that the stronger ionic
strength of ionic liquids suppressed the alkylation reaction
DSmax.=0.64
Cellulosic PILs
Scheme 1. Facile preparation of cellulosic PILs by using although a homogeneous state was sustained all the time.
chlorinated cellulose and 1-methyl-imidazole.
Table 1. Preparation of [Cellmim][Cl] under various conditons
Entry
Solvent
T
C
t
h
N
%
DS
Yield
%
RE
%
o
Inspired by the commonly used protocol for the
preparation of imidazolium ILs (Scheme 1), herein, we report a
facile protocol for the preparation of cellulosic PILs, cellulose
anchored 1-methyl-imidazolium chloride ([Cellmim][Cl]), via
alkylation reaction between chlorinated cellulose and 1-
methyl-imidazole. The as-prepared cellulosic PILs were applied
1
2
3
4
5
6
none
none
none
none
80
24 2.049
24 5.003
24 6.976
48 7.752
72 4.751
24 5.517
24 4.176
0.14
0.37
0.56
0.64
0.35
0.42
0.30
79.3
89.6
83.5
84.5
97.5
89.2
84.4
15.7
41.6
62.9
71.9
39.3
47.2
33.7
90
100
100
90
in the cycloaddition of CO to epoxides under solvent-free
2
conditions as a proof and concept application.
b
DMSO
Cellulose was chemically modified with SOCl to obtain
2
b
chlorinated cellulose (6-chloro-6-deoxycellulose, CDC) with a
DS of 0.89 preferentially on C-6 position, which was in
DMSO
100
90
c
35, 36
7
AmimCl
accordance with previous publications
. Compared with
a
b
c
other classes of ionic liquids the imidazolium-based ionic
liquids are one of the most important families of ionic liquids
0
.5 mL 1-methyl imidazole, 0.5 g CDC, 0.5 mL DMSO; 12.5 g
AmimCl;
1
due to their outstanding properties . We started the study
with 1-methyl-imidazole to prepare the [Cellmim][Cl] both
without solvent and in DMSO or 1-allkyl-3-methyl-imidazolium
chloride (AmimCl). The degree of substitution (DS) of the
The solubility of [Cellmim][Cl] with different DS values in
conventional solvents was also studied (Table S1). Their
solubility mostly depends on the DS values and the samples
with DS>0.37 are soluble in water; the sample with a DS of
[
Cellmim][Cl] was calculated according to elemental analysis
results of nitrogen content and the reaction efficiency (RE) was
calculated from the DS of CDC and the [Cellmim][Cl]. It was
0
.14 only can be swollen by water, but is soluble in DMSO. It is
also interesting to find that the samples with DS<0.4 are
soluble in DMSO; while the samples with DS>0.4 can be only
swollen by DMSO, thus achieving a gel-like solution with
enhanced viscosity. It is worthy to mention that the good
solubility of the [Cellmim][Cl] in water and DMSO will provide
great opportunities to prepare functional composites materials
with other functional components through solution processing
and homogeneous catalysis.
found that the alkylation reaction could proceed smoothly at
o
1
00 C, and [Cellmim][Cl] with a DS of 0.56 was obtained in 24
h when excess 1-methyl-imidazole was used as a reagent and
solvent (Table 1, entry 3). Further prolonging the reaction time
to 48 h, a maximal DS of 0.64 was achieved (Table 1, entry 4).
Correspondingly, the RE of the chloromethyl on cellulose was
7
1.9%. Although the DS increased significantly, the yield did
not change notably, which suggested that degradation of the
chlorinated cellulose occurred during the reaction. The
reaction temperature has an great affect on the reaction,
which was evidenced by the DS significantly decreased to 0.37
The successful preparation of chlorinated cellulose and
13
[
Cellmim][Cl] was confirmed by comparative CP/MAS C NMR
spectra as shown in Figure 1. The spectrum of pure cellulose
show typical peaks for its six carbons in the monomer unit. The
downfield peak at 104.7 ppm is assigned to C-1 since C-1 is
bonded to two oxygen atoms. The peak at 88.6 ppm is
assigned to C-4 which is connected to only one oxygen and is
responsible for β-1,4-glucoside bonds. The chemical shift at
o
and 0.14 when the temperature was decreased to 90 C and
o
8
0 C in 24 h, respectively (Table 1, entries 1, 2). It was also
found that the reaction started in heterogeneous conditions
and then became highly swollen gel-like state with high
viscosity, which confirmed the successful alkylation reaction. In
order to decrease the viscosity of the reaction mixture, DMSO
and AmimCl were used as solvents for the alkylation reaction
under identical conditions. It was interesting to find that the
reaction mixture was also heterogeneous at the beginning in
the case of DMSO, but became homogeneous in shorter time.
7
4.7 and 72.0 ppm are classified to C-2, C-3 and C-5 because
they are all secondary carbons attached to –CH or –OH group.
The peak of C-6 appears at 65.0 ppm, which is a primary
carbon connected to –OH and –CH2 groups. The partial
substitution of the –OH by chloride at C-6 resulted in a
significant change of the chemical shift of C-6 from 65.0 to
44.8 ppm. The substitution only resulted in slight changes of
Although higher yields were obtained in this case, the
o
[
Cellmim][Cl] only have moderate DS of 0.35 and 0.42 at 90 C
2
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the chemical shifts of C-1 from 104.7 to 103.7 ppm, of C-4
from 88.6 to 83.9 ppm, while no notable affect on the
chemical shifts of C-2, C-3 and C-5 was observed. These results
confirm the successful preparation of chlorinated cellulose in
a
View Article Online
DOI: 10.1039/C5RA05667E
b
7
52 723
c
C-Cl
a
3
7
this study .
1
577
CH3
1
114 1064
b
c
N
N
2 3 5
Cl
R
=
-OH, -Cl or
8
10
R
6
9
N
Cl-
4000
3500
3000
2500
2000
1500
1000
500
5
10
15
20
25
30
35
40
45
50
5
O
N
7
-1
4
Wavenumber (cm
)
O
8 9
10
2 degree
HO
3
2OH
1
1
6'
n
7
DS = 0.64
4
6
Fig. 2 FTIR and X-ray diffraction patterns of cellulose (a), CDC (b,
c
DS=0.89) and [Cellmim][Cl]DS=0.64 (c).
Cl
6
5
O
The changes of the molecular-level aggregation structure
of the polymer arose by the chemical modifications could be
followed by X-ray diffraction technology. The X-ray diffraction
pattern of raw cellulose shows three distinctive peaks
corresponding to 101, 002 and 040 planes which are
characteristic of microcrystalline cellulose (Fig. 2) . In contract,
the chlorinated cellulose exhibits new crystal peaks but with
lower intensity, different from those observed for raw
4
6
O
1
HO
2OH
1
3
4
n
b
OH
5
1
6
3
O
4
6
35
O
4
HO
2OH
1
n
a
2
00
180
160
140
120
100
80
60
40
20
0
cellulose, which indicate that new assembly is formed via the
ppm
35, 37
bonded chlorine atoms and remaining hydroxyl groups
.
13
Fig. 1 CP/MAS C NMR spectra of cellulose (a), CDC (b, DS=0.89)
and [Cellmim][Cl]DS=0.64 (c).
The decreased crystallinity of chlorinated cellulose will be very
interesting mainly when subsequent modification are intended,
such as anchoring a 1-methyl-imidazolium moiety to the
backbone. For the [Cellmim][Cl]DS=0.64, as shown in Figure 2, a
drastic decrease in crystallinity was observed in comparison
with the raw cellulose and CDC. These data suggest that the
cellulosic PILs have an amorphous structure, and the newly
anchored groups do not establish an ordered assembly.
With the covalent bonding the 1-methyl-imidazolium
chloride moiety onto cellulose, new signals at 35.9 (C-10),
23.2 (C-8, 9), and 137.6 (C-7) appeared, assigning to the
1
imidazolium ionic liquids moiety, and the reaction resulted in a
change in the chemical shift of C-6 from 44.8 to 50.3 ppm, and
no obvious affect on the chemical shifts of C1-C5 carbons. A
signal of chloromethyl carbon were still detected in the spectra
of [Cellmim][Cl]DS=0.64, indicating the presence of chloromethyl
residual, which was in accordance with the fact that the DS of
ionic liquids moiety is lower than the DS of chlorinated
cellulose. We further applied the muli-peaks analysis using
Lorentzian method in Origin software to separate the
overlapped peaks (Fig. 1-c, C6, C6’) and calculate the
corresponding areas. By compare the areas of the separated
peaks, the DS value of methyl imidazolium chloride and
chloride is estimated to be 0.64 and 0.36, respectively. The
results are in good accordance with the elemental analysis.
The structure of [Cellmim][Cl]DS=0.64 was further confirmed by
Further thermogravimetric analysis of cellulose, CDC and
[
Cellmim][Cl]DS=0.64 were shown in Figure 3. Both of cellulose
derivatives exhibited inferior thermal stability to the raw
cellulose, as illustrated in thermogravimetric curves. Cellulose
o
can remain stable up to 300 C and shows only one
o
decomposing process from 300 to 380 C with a mass loss of
9
2% owing to the pyrolytic degradation of the carbon skeleton.
The onset degradation temperature of CDC and
o
[
Cellmim][Cl]DS=0.64 is 266 and 220 C, respectively, and their
o
mass loss even after 600 C is estimated to be 83% and 71%,
respectively. The lower degradation temperature was
attributed to the destroyed crystalline structure and the
different chemical structures. In addition, both CDC and
HSQC in D O (Fig. S1), and the assignments was summarized in
Table S2. The results are in accordance with that of solid state
C NMR.
The successful chemical modification of cellulose was also
confirmed by FTIR analysis (Fig 2). In comparison with the
2
[
Cellmim][Cl]DS=0.64 gave two stage of decomposition behavior.
o
13
For CDC the first mass loss between 150 and 250 C is caused
1
00
100
80
60
40
20
0
a
b
8
6
4
2
0
0
0
0
0
-1
c
spectrum of raw cellulose, two new bands at 752 and 723 cm
appeared in the spectrum of the chlorinated cellulose, which
were corresponded to stretching vibration of the C-Cl bond. In
association with the appearance of the new bands, the bands
from 1500 to 1200 cm decreased owing to the substitution of
the hydroxyl group on C-6 . In contrast, new characteristic
-1
3
7
-20
-40
-20
-40
c
b
a
-1
bands centered at 1577, 1114, and 1065 cm corresponded to
the imidazolium moiety appeared in the spectrum of
100
200
300
400
o
C
500
600
Temperature
38
Fig. 3 TGA-DTG curves of cellulose (a), CDC (b, DS=0.89) and
[
Cellmim][Cl]
, and the intensity of the band centered at
DS=0.64
[
Cellmim][Cl]DS=0.64 (c).
-
1
3
400 cm increased due to the hydrophilic property of the 1-
methyl-imidazolium chloride moiety.
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o
Tm = 119.27
C
Table 2. Cycloaddition of CO with different epoxides catalyzed by
2
A
B
View Article Online
exo
Hm = 2.716 J/g
a
exo
[
Cellmim][X]
DOI: 10.1039/C5RA05667E
a: 1st
b: 2nd
a: 1st
b: 2nd
b
Entry
Catalysts
Epoxide
Product
Yield%
o
O
a
o
Tc = -11.92 C
Tc = -19.64
C
a
O

Hc = -0.193 J/g
H
c
= -0.469 J/g
b
1
[Cellmim][Cl]DS=0.64
O
O
O
O
O
O
O
O
44.2
b
o
Tg = -40.29 C (I)
O
O
O
-
50
0
50
o
100
150
-50
0
50
o
100
150
O
O
Temperature ( C)
Temperature ( C)
2
3
[Cellmim][Br]DS=0.64
[Cellmim][I]DS=0.64
[Cellmim][I]DS=0.64
68.7
80.4
95.1
Fig. 4 DSC curve of CDC (DS=0.89, A) and [Cellmim][Cl]DS=0.64 (B). a:
first heating cycle, b: second heating cycle.
by the cleavage of C-Cl bond and the condensation of hydroxyl
groups on C-2 and C-3. The second stage from 250 C is
corresponding to the depolymerization of cellulose polymeric
o
O
c
3
9, 40
4
chain
. The degradation behavior of [Cellmim][Cl]DS=0.64 is
similar to that of CDC, with the initial mass loss from 220 to
O
o
O
2
80 C which can be interpreted as losing of the immobilized
5
6
[Cellmim][Br]DS=0.64
[Cellmim][I]DS=0.64
O
87.4
88.7
O
imidazulium group on cellulose backbone together with the
condensation of hydroxyl groups on C-2 and C-3. The second
step is also correlated with the loss of cellulose fiber.
Cl
Cl
O
O
O
O
Br
Br
The thermal properties of the as-prepared cellulose
derivatives were further investigated by differential scanning
calorimetry. The CDC exhibits typical crystal structure with
O
O
O
7
[Cellmim][I]DS=0.64
O
O
95.3
91.7
Ph
O
o
Ph
melting peak at 119.27 C and the corresponding enthalpy is
O
O
2
.716 J/g from the first heating cycle (Fig. 4 A). Additionally,
O
o
O
8
[Cellmim][I]DS=0.64
the crystallization temperature (T ) appeared at -19.64 C with
c
Δ
H value of -0.193 J/g. The glass transfer temperature was
c
o
a
observed from the second heating cycle at -40.29 C. On the
other hand, the [Cellmim][Cl]DS=0.64 was found to be
amorphous but the obvious grass transition stage was not
Reaction conditions: epoxides 20 mmol, 5 mol% Cellulosic PILs,
o b C o
CO pressure 2 MPa, 120 C 6 h; isolated yield; 150 C
2
CO , and good isolated yields of cyclic-carbonates were
achieved.
observed in neither first nor second heating curve (Fig. 4 B).
2
o
The T of [Cellmim][Cl]
appeared at -11.92 C with
Δ
Hc
c
DS=0.64
The reusability of the [Cellmim][I]DS=0.64 catalyst was
studied in the cycloaddition of glycidyl phenyl ether and CO2.
value of -0.469 J/g from the first heating cycle.
The design and preparation of PILs have been
demonstrated to broaden the properties and applications of
ionic liquids, which have been reviewed in recent
The catalyst could be separated by washing with ethyl acetate,
filtered and then dried under vacuum. The recovered catalyst
was directly employed for the cycloaddition under identical
conditions. The catalyst remained active up to 5 runs without
remarkable decrease in yield demonstrating high reusability of
the catalyst (Fig. 5). Further analysis of the recovered catalyst
4, 5, 7, 41
comprehensive reviews
. With the new cellulosic PILs
([Cellmim][Cl]) in hand, it is reasonable to conjecture that its
physical and chemical properties can be tuned via the freedom
combination of this cellulosic poly(cation) and anions due to
the designable nature of the anchored 1-methyl-imidazolium
1
by FTIR, H NMR and TGA were performed towards a better
42-44
understanding of the potential structural changes on the
catalyst during the reusability study, and the comparative
results were shown in Figure S2 to S4. The structural
chloride moiety
. The direct use of PILs as catalysts or as the
supports for catalytic active species in various catalytic
7-10
reactions has been widely investigated . Among the various
reactions catalyzed by PILs, one of the most concerned topics
is the synthesis of cyclic carbonates via its addition reaction of
1
information from the H NMR and FTIR spectra of the
recovered catalyst demonstrated that the chemical bonded
imidazolium moiety was stable during the reaction, and the
8
-10, 27, 42
CO and epoxides
. Therefore, the reaction was also
proof and concept application of the
Cellmim][Cl]DS=0.64 to demonstrate its potential. To our delight,
2
structure remained unchanged after
5
cycles, which
selected as
a
determined its stable catalytic activity during the reusability
study. The TGA result (Figure S4) showed that the onset
temperature of recovered catalyst remained unchanged but
[
the catalytic activity varied with the halide anion (Table 2), and
iodide exhibited the highest yield while chloride showed the
o
the residual weight at 650 C decreased from 38.9% to 31.0%.
lowest yield in the cycloaddition of CO to propylene oxide.
2
The possible reason for this is still unclear at the early stage of
the study.
The difference may be ascribed to the different nucleophilicity
and leaving ability of the halide anions, which is in accordance
with the trend in previous studies . The catalytic system could
also be extended to the reactions of different epoxides with
45
4
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1
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Run
Fig. 5. Reusability of [Cellmim][I]DS=0.64. Reaction conditions: glycidyl
phenyl ether (20 mmol), [Cellmim][I]DS=0.64 (5 mmol%), 120 C, 2
o
2
2
MPa, 6 h.
In summary, the chemical modification of cellulose with
SOCl produced CDC with a DS of 0.89, which was successfully 24 M. Hashem, P. Hauser and B. Smith, Text. Res. J., 2003, 73,
2
1
017-1023.
used as alkylation reagent for 1-methyl-imidazole to synthesize
cellulosic PILs with tunable substitution degrees. The structural
and thermal properties of the cellulosic PILs were studied by
various technologies, and they were ready for the preparation
2
2
5 H. S. Seong and S. W. Ko, J. Soc. Dyers Colour., 1998, 114,
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24-129.
6 K. R. Roshan, T. Jose, A. C. Kathalikkattil, D. W. Kim, B. Kim
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efficient and recyclable catalysts for the cycloaddition of CO2
to epoxides under solvent-free conditions. Further work in this
area will focus on the design and application the derivative
functional materials by taking the advantages of cellulose and
ionic liquids moieties.
2
8 N. Clousier, A. Filippi, E. Borré, E. Guibal, C. Crévisy, F. Caijo,
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Acknowledgements
This work was supported by Natural Science Foundation of
China (no. 21002101).
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DOI: 10.1039/C5RA05667E
Graphical Abstract
Cellulosic Poly(ionic liquid)s: Synthesis, Characterization
and its Application in the cycloaddition of CO to Epoxides
2
Cellulosic poly(ionic liquid)s (PILs) were prepared via nucleophilic substitution of chlorinated
cellulose by 1-methyl-imidazole and their structure and thermal properties have been fully
characterized, which were ready for the preparation of novel green cellulosic catalytic and
functional materials.