Rcents Progrs en Gnie des Procds, Numro 94 - 2007

ISBN 2-910239-68-3, Ed. SFGP, Paris, France

Green Technology for Cellulose Processing in Ionic Liquids

the Effect of Ultrasound

MIKKOLA Jyri-Pekkaa, KIRILIN Alexeya,b, MURZIN Dmitry Yu.a and SALMI Tapioa

Laboratory of Industrial Chemistry - Process Chemistry Centre Department of Chemical Technology

Faculty of Technology bo Akademi University
Biskopsgatan 8 - 20500 bo-Turku Finland
jpmikkol@abo.fi
b

Mendeleev Institute of Chemical Technology

Moscow Russia

Abstract
Ionic liquids 1-allyl-3-methylimidazolium chloride [Amim][Cl] and 1-butyl-3-methylimidazolium
chloride [Bmim][Cl] were utilized in the dissolution of different natural cellulose biopolymers. The
biopolymers subject to this investigation were Aldrich microcrystalline cellulose, cotton linters and Kraft
cellulose cutted to 0.35 mm fibers from a pulpmill (Mets-Botnia, Finland). In addition, high-intensity
sonication by means of an ultrasonic horn system was applied. Both ionic liquids were able to dissolve
cellulose at elevated temperatures in significant concentrations, although significant differences were
observed depending on the type of cellulose and ionic liquid. Moreover, the dissolution process under
conventional heating was rather slow, typically several hours. Upon use of high power ultrasound the
dissolution process was dramatically faster and, optimally, the dissolution proceeded in a matter of few
minutes only.
Key-words : ionic liquids cellulose ultrasound - dissolution

1. Introduction
Non-derivatising dissolution of cellulose, the most abundant biopolymer on earth, has been a challenge
for a long time. Processing of cellulose is traditionally carried out in aqueous milieu although it really
cannot dissolve cellulose. As a consequence, the reaction rates of various transformations leading to
functionalized derivatives such as cellulose carboxylates, laurates and acetates are heavily retarded due to
the slow mass transfer in the aqueous cellulose slurry. Alternative solvent systems, like LiCl/N,Ndimethylacetamide (DMAc) (Terbojevich et al. (1985), Dawsey et al. (1990), Nishio et al. (1988) and
Nishino et al. (2004), LiCl/N-methyl-2-pyrrolidine (NMP) (Edgar et al. (1995)), LiCl/1,3-dimethyl-2imidazolidione (DMI) (Tamai et al. (2004)), DMSO/paraformaldehyde (PF) (Masson et al. a. and b.
(1991)), N-methyl-morpholine-N-oxide (NMMO) (Heinze et al. (2001)) and molten salt hydrates such as
LiClO4.3H2O, LiSCN.2H2O (Fischer et al. (1999) and Hattori et al. (2002)) have limitations due to their
volatility, toxicity, cost-, instability and recovery issues. Only the NMMO/H2O system (Kwon et al.
(2006)) has been applied in industrial operations, regardless of the disadvantages associated with its use
(high temperatures and costs as well as cellulose degradation).
Room-temperature ionic liquids (RTILs or ILs) containing especially Cl- anions are known to be capable
of dissolving different types of cellulose under heating (Zhang et al. (2005); Huddleston et al. (2001) and
Swatloski et al. (2002)). In addition, a few other imidazolium ionic liquids, such as those with an acetate
(Leng et al. (2006)) or a bromide (Dorn et al. (2006)) anion have been found to dissolve cellulose. This
study was commenced in order to investigate whether high power ultrasound is capable of enhancing the
dissolution process.

2. Experimental
Reagents (1-methylimidazole, 1-chlorobutane, allylchloride) were purchased from Aldrich and utilized
without further purification. Solvents (ethyl acetate, toluene) were freshly distilled by standard
procedures. All the manipulation concerning dissolution of cellulose samples were carried out under

1-9

Rcents Progrs en Gnie des Procds, Numro 94 - 2007

ISBN 2-910239-68-3, Ed. SFGP, Paris, France

normal atmosphere. Sonication was carried out by a high-intensity ultrasonic generator with an adjustable
power output (0-100 W, nominal power) coupled to a titanium horn (AEA Technologies, UK). A constant
power adjustment of 10% (10 W) was applied in all experiments with on-line sonication. Since very
intensive cavitation and, consequently heating, was induced in the ionic liquid samples, NMR spectra of
the pure ionic liquids subject to ultrasonic field were recorded. Moreover, the recovered ionic liquids
utilized in cellulose dissolution experiments were subject to NMR analysis. The purpose was to determine
whether the ionic liquids suffered from thermal degradation.
NMR spectra were recorded on Bruker AV-600 or Bruker AC-250 equipments. Thermogravimetric
analysis (TGA) data were obtained on a Cahn Balance Stand using a programmed temperature ramp from
25C to 450C, at 10C min1, under an atmosphere of dry N2. TMS derivatives after acid methanolysis
were analyzed on a Varian 3400 Gas Chromatograph (GC) equipped with a Flame Ionization Detector
(FID), a capillary column (HP-1, 25 m x 0.2 mm) and a Varian 8200 autosampler. The temperature
program utilized was as follows: 100C, 4C/min, 175C, 12C/min, 290C, 5 min. The carrier gas was
H2 and the injection volume 0.7 L. Differential Scanning Calorimetry (DSC) curves were recorded on
TA Instruments Q1000 using programmed heating at 10C/min under an atmosphere of N2 in an
aluminium pans, a cooling rate was 5C/min and a cooling accessory being glycol. Scanning Electron
Microscopy (SEM-EDX) was utilized to obtain images of fresh and recovered cellulose samples from
ionic liquids (samples were coated with coal before analyses).
2.1 Sonication of pure [Amim][Cl]
[Amim][Cl] (1 g) was placed into a vial and the horn of the ultrasonic device was inserted into the liquid
at a depth of a of the liquid phase. Then ultrasonication treatment (10% of max. power) was conducted
for 10 min. 1H NMR, H (600.13 MHz, CD3OD); 9.00 (1H, s, C(2)H), 7.63 (2H, m, C(4)H and C(5)H),
6.10 (1H, m , NCH2CH=CH2), 5.42-5.47 (2H, m, NCH2CH=CH2), 4.88 (2H, d, 3J 6.54 Hz,
NCH2CH=CH2), 3.97 (3H, s, NCH3). 13C NMR, C (150.92 MHz, CD3OD); 130.66, 123.69, 122.24,
120.47 (2C), 51.38, 35.16. Decomposition temp acc. to TGA (under N2): 273-275C; lit. 273C, Zhang et
al. (2005).
2.2 Preparation of 1-allyl-3-methylimidazolium chloride [Amim][Cl]
To a three neck round-bottom flask (flushed with argon for 10 min beforehand), equipped with a reflux
condenser and a magnetic stirrer, allylchloride (10 mL, 122.37 mmol) and N-methylimidazole (8 mL,
97.39 mmol) were inserted via syringe (at room temperature). The mixture was stirred at 55-60C for 24
hours. The viscous liquid of slight amber colour formed. The product was dried at a vacuum (25 mbar,
80C, 24 hours; 1.6 mbar, 80C, 30 min). 1H NMR, H (600.13 MHz, CD3OD); 9.16 (1H, s, C(2)H), 7.74
(1H, d, 3J 7.44 Hz C(4)H), 7.73 (1H, d, 3J 7.44 Hz C(5)H), 6.15 (1H, m, NCH2CH=CH2), 5.45-5.51 (2H,
m, NCH2CH=CH2), 4.98 (2H, d, 3J 6.25 Hz, NCH2CH=CH2), 4.04 (3H, s, NCH3). 13C NMR, C (150.92
MHz, CD3OD); 130.99, 123.80, 122.32, 120.57 (2C), 51.40, 35.46. Decomposition temp acc. to TGA
(under N2): 273-275C; lit. 273C, Zhang et al. (2005).
2.2 Preparation of 1-butyl-3-methylimidazolium chloride [Bmim][Cl]
To a three neck round-bottom flask (flushed with argon for 10 min), equipped with reflux condenser and
a magnetic stirrer, toluene (7 mL) was transferred via syringe. N-methylimidazole (14 mL, 0.175 mmol)
and 1-chlorobutane (20 mL, 0.192 mmol) were added via syringe under argon flushing. The mixture was
placed in an oil bath (80C) and stirred for 24 hours. After cooling to room temperature, the mixture was
placed to a freezer (-20C) for 24 hours. The top layer (toluene) was decanted under a flow of argon and
EtOAc was added. A mixture consisting of two layers (top layer EtOAc and unreacted starting materials;
bottom product layer) was shaken several times and again placed into the freezer (-20C) for 72 hours,
upon which white crystals of [Bmim][Cl] formed. Under a flow of argon EtOAc was decanted, the salt
filtered off and washed with cool EtOAc (3x50 mL). The resulting white crystals of [Bmim][Cl] were
dried on a rotary evaporator (20 mbar, 35C, 5 hours; 2 mbar, 25C, 14 hours) yielding 92% of the
desired product. 1H NMR, H (250.13 MHz, acetone-d6); 10.66 (1H, s, C(2)H), 8.10-8.05 (2H, m, C(4)H
and C(5)H), 4.61 (2H, t, 3J 7.1 Hz, NCH2CH2CH2CH3), 4.26 (3H, s, NCH3), 2.21 (2H, m,
NCH2CH2CH2CH3), 1.52 (2H, m, NCH2CH2CH2CH3), 1.07 (3H, t, 3J 7.3 Hz, NCH2CH2CH2CH3). 13C

2-9

Rcents Progrs en Gnie des Procds, Numro 94 - 2007

ISBN 2-910239-68-3, Ed. SFGP, Paris, France

NMR, C (62.90 MHz, acetone-d6); 144.20, 124.29, 123.18, 49.88, 36.56, 33.00, 20.05, 13.85.
Decomposition temperature according to TGA 253-255C; lit. 254C, Huddleston et al. (2001).
4
5
4
5

N
2

Figure 1. 1-allyl-3-methylimidazolium.

N
2

Figure 2. 1-butyl-3-methylimidazolium.

2.3 General procedure for cellulose dissolution in ILs

At first, preliminary experiments were carried out in which cellulose samples (Aldrich, microcrystalline,
20 micrones) were dried under vacuum (24 mbar, 80C, 5 hours; 4.1 mbar, 80C, 4 hours). Since no
differences in the dissolution times were observed between predried and non-dried samples, all
subsequent experiment were carried out with as received samples.
The cellulose sample (50 mg, 5 wt%) and IL ([Amim][Cl]or [Bmim][Cl], 1 g) were inserted into a vial.
Subsequently, the horn of the ultrasonic device was inserted into the liquid, as described earlier. The
ultrasonic treatment (US) was commenced until the whole cellulose sample had dissolved (visible
obervation). In order to be sure that complete dissolution had taken placed, the ultrasonic treatment was
continued for still 1 minute more. After this the cellulose sample was recovered according to the
procedure described below and analyzed by methanolysis following with GS-MS, SEM, TGA and DSC.
The IL was recovered and analysed by means of NMR on nuclei 1H and 13C as well as TGA.
2.4 General procedure for recovering of cellulose samples and IL
To a hot solution of 5 wt% cellullose dissolved in an ionic liquid, a portion of absolute EtOH (99.5+, ca.
1-2 mL, Primalco Oy) was added. A gel-like mass formed which was placed into an evaporating glass and
an additional portion of EtOH (20 mL) was added. After stirring at 60C for 20 min, EtOH was decanted
via pasteur pipette and a new portion of EtOH was added. The procedure was repeated 3 times. After the
last cycle the glass was placed into a freezer (-20C) for 2 hours resulting into a complete cellulose
precipitation on the bottom.
[Amim][Cl] recovery: collected EtOH (ca. 80 mL) eluents was placed in a flask coupled to a rotary
evaporator (20 mbar, 25C, 5 hours; 3 mbar, 25C, 30 min), resulting into a pure ionic liquid. 1H NMR,
H (600.13 MHz, CD3OD); 9.09 (1H, s, C(2)H), 7.66-7.69 (2H, m, C(4)H and C(5)H), 6.13 (1H, m,
NCH2CH=CH2), 5.45-5.49 (2H, m, NCH2CH=CH2), 4.93 (2H, d, 6.22 Hz, NCH2CH=CH2), 4.00 (3H, s,
NCH3). 13C NMR, C (150.92 MHz, CD3OD); 130.82, 123.74, 123.04, 120.53 (2C), 51.40, 35.32.
Decomposition temp according to TGA (under N2): 272-274C ; Lit. 2730C ; Zhang et al. (2005).
[Bmim][Cl] recovery: In the case of [Bmim][Cl], a EtOH:acetone 1:3 mixture was used. 1H NMR, H
(250.13 MHz, acetone-d6); 10.52 (1H, s, C(2)H), 8.14-8.08 (2H, m, C(4)H and C(5)H), 4.61 (2H, m,
2.21 (2H, m, NCH2CH2CH2CH3), 1.52 (2H, m,
NCH2CH2CH2CH3), 4.26 (3H, s, NCH3),
NCH2CH2CH2CH3), 1.07 (3H, m, NCH2CH2CH2CH3). 13C NMR, C (62.90 MHz, acetone-d6); 148.14,
124.39, 123.22, 49.88, 36.59, 32.21, 20.07, 13.84. Decomposition temperature according to TGA (under
N2) 253-255C ; lit. 254C, Huddleston et al. (2001).
Cellulose recovery: The precipitated cellulose was collected and placed into a rotary evaporator (20 mbar,
25C, 5 hours; 3 mbar, 40C, 30 min) resulting in dry cellulose.
2.5 Dissolution of cellulose in regenerated [Amim][Cl]
Regenerated [Amim][Cl] (1 g) was placed into a vial and cellulose sample (50 mg, Aldrich,
microcrystalline, 20 micron) was added. The procedure similar to the one already described was
peformed. Afer complete dissolution the components were recovered as described earlier. The recovered
materials were characterized as previously described.

3-9

Rcents Progrs en Gnie des Procds, Numro 94 - 2007

ISBN 2-910239-68-3, Ed. SFGP, Paris, France

3. Results and discussion

Room-temperature ionic liquids (RTILs or ILs) such as [Bmim][Cl] and [Amim][Cl] were capable of
dissolving different types of cellulose under conventional heating. Furthermore, this dissolution process
can be considerably speeded up by means of high-intensity ultrasound. The dissolution of the cellulose
was conducted under sonication (10 W nominal power; 10% of max. power). Initial expreriments
demonstrated the feasibility of cellulose dissolution in [Amim][Cl] under the experimental conditions. 5
wt% (of the IL weight) cellulose powder was dissolved completely in 2 minutes only upon ultrasound
enhanced dissolution procedure!
According to the data obtained from methanolysis and GS-MS of the recovered cellulose sample, the
cellulose bulk was completely dissolved in the ionic liquid. One of the cellulose types used in this study,
microcrystalline Aldrich cellulose, is a crystalline polymer. On the basis of the analysis, during the
process of dissolution and further recovery procedure, cellulose must have lost its crystallinity and,
instead, restructured itself into a mostly amorphous form. Direct evidence was provided by methanolysis
and GS-MS. Since only amorphous part of the recovered sample can undergo methanolysis, this method
is a convenient method to study the degree of crystallinity in a sample. A comparison of chomatograms
obtained for initial (even crystalline cellulose always contains amorphous part or hemicellulose which can
undergo methanolysis) and recovered cellulose samples demonstrated no differences and, therefore, it can
be concluded that no chemical changes occurred during the process of dissolution under conventional
heating or ultrasound enhanced procedure. After it was concluded that 5 wt% microcrystalline cellulose
was, indeed, possible to reversibly dissolve in the two ionic liquids utilized in this study, all further
experiments concerning the investigation of the structure and morphology of the cellulose samples were
carried out on cotton linter, this being an interesting type of cellulose due to its fiber structure and
extreme low solubility. Likewise, the solubility of Kraft pulp from a Finnish pulp mill (Mets-Botnia,
0.35 mm) was evaluated and the results are summarized in the table 1.
Table 1. The determination of dissolution limits and time for different types of cellulose in [Amim][Cl]
[Bmim][Cl] upon ultrasound enhanced dissolution process.

and

Entry

Ionic liquid

Cellulose type

Dissolution
time, min

Amount,
wt%

[Amim][Cl]

Microcrystalline, Aldrich

22

27

[Amim][Cl]

cotton linter

22

13

[Amim][Cl]

Kraft pulp, 0.35 mm

[Bmim][Cl]

Microcrystalline, Aldrich

10

[Bmim][Cl]

cotton linter

17

10

[Bmim][Cl]

Kraft pulp, 0.35 mm

As can be seen, [Amim][Cl] displays better dissolving abilities than [Bmim][Cl]. Regardless of the fact
that [Bmim][Cl] can dissolve up to 25 wt% of cellulose under heating supported by short microwave
pulses while only 14.5 wt% solution of cellulose can be obtained in [Amim][Cl], during ultrasound
enhanced dissolution procedure this situation changes dramatically: A solution containing up to 27% of
microcrystalline cellulose can be easily obtained in [Amim][Cl] and periodic ultrasound pulses (1 min. of
sonication followed by a 1 min. pause, entry 1). It is noteworthy that the solubility limits reported by
Zhang et al.13 in [Amim][Cl] were exceeded. In comparison with conventional heating the dissolution
time decreases profoundly. For instance, to obtain a 5 wt% of cellulose in [Amim][Cl] using conventional
heating, 1 hour (or even more) is required, complete dissolution can be achieved in only 2 minutes upon
ultrasound enhanced dissolution. Upon dissolution experiment with other types of cellulose, the two ionic
liquids demonstrated relatively small differences: 13 wt% and 10 wt% solution of cotton linter in
[Amim][Cl] and [Bmim][Cl] could be obtained in 22 and 17 min., respectively. Moreover, the dissolution
of 8 wt% and 9 wt% of Kraft pulp (0.35 mm) in [Amim][Cl] and [Bmim][Cl] took 5 and 7 min,
respectively. As an observation one can further report that cotton linter cellulose dissolves slowly in

4-9

Rcents Progrs en Gnie des Procds, Numro 94 - 2007

ISBN 2-910239-68-3, Ed. SFGP, Paris, France

temperature, C

[Amim][Cl] at room temperature in

150
around 2 weeks. During sonication
prominent and rapid heating of the
120
reaction mixture was occuring. The
temperature in the system approached
150C. In order to investigate the kinetics
90
of the temperature rise inside the vial the
temperature was monitored by means of
60
an infrared thermometer. The temperature
vs. time dependency is illustrated by Fig.
30
3.
The temperature rises swiftly from
0
1
2
3
4
5
ambient to 150C in 2.5 min due to
time, min
intense cavitation. It is worth to mention
Figure 3. Reaction temperature vs. time upon sonication of
that after this temperature was reached (in
cellulose in [Amim][Cl] (nominal power input 10 W).
2.5 min.), the temperature remained
constant at this plateau in all experiments.
The thermal decomposition temperatures of these ionic liquids, [Amim][Cl] and [Bmim][Cl], have the
decomposition temperatures readily above this temperature, 273C and 254C, respectively. The
decomposition temperatures of cellulose samples investigated in this study were found to be in the range
of 270 to 310C. Therefore, no thermal degradation of either cellulose or the ionic liquid samples was
expected. Indeed, thermal pyrolysis could be possible upon contact to the horn of the ultrasonic device.
No doubt both temperature and acoustic cavitation, make their own contribution to the process of
dissolution and this two effects cannot be separated. Nevertheless, in the study of Leng and Mormann
(Leng et al. (2006)), they claimed that in a few hours cotton linter, Avicel PH 101 and hydrocellulose
degraded to the oligomer level at 1500C in [Bmim][Cl], [Bmmim][Cl] (1-butyl-2,3-methyl imidazolium
chloride) and [Bmim][OAc] (1-butyl-3-methylimidazolium acetate) ionic liquids. It was claimed that the
degradation is caused by hydrolysis and not by thermal processes. However, in our case the cellulose
samples were generally rapidly dissolved after which the temperature was allowed to drop. Thus, we did
not observe detectable degradation of cellulose.
In order to investigate whether any thermal pyrolysis or degradation of ionic liquids under acoustic
streaming takes place, [Amim][Cl] was exposed to sonication for a period of 10 min. It was observed that
the colour of [Amim][Cl] changed from slight amber to strong tea during this time. However, NMR
spectra gave no evidence of sample degradation confirming the purity of ionic liquid. A conceivable
reason for a rather strong change of colour could be a penetration of Tin+ ions (the titanium US horn is
known to degrade slowly upon use) into the layer of [Amim][Cl]. A comparison of NMR spectra of
freshly prepared, sonicated and recovered (from cellulose dissolution experiments) [Amim][Cl],
demonstrated no difference in the chemical structrure. The purity of regenerated [Bmim][Cl] was also
confirmed by NMR spectroscopy, indicating neither changes in the chemical structure nor presence of
any contaminants.

4. Characterization results
As already mentioned, no chemical transformations took place during the dissolution-recovery procedure
of the cellulose samples. Thus, in order to verify whether any changes of the polymeric structure took
place in terms of the morphology or physical properties, various characterization methods were applied.
SEM images of fresh and recovered cotton linter and microcrystalline cellulose (Aldrich and kraft pulp)
are displayed in Fig 4. A rupture of fibres can be observed on the right picture (cotton linter recovered
from IL) supporting the conclusion that complete dissolution of the sample took place. The light spots on
the right picture can be assigned to a small contamination by ionic liquid. According to the data obtained
by SEM-EDX, the contamination level is roughly about 1-1.5 wt%. Other tiny spots on the image can be
assigned to Ti ions, which as already discussed, may be present in the ionic liquid, too. Looking at e.g. the
last pair of images in Fig.4, it is evident that the fibers have partially fused together, forming an

5-9

Rcents Progrs en Gnie des Procds, Numro 94 - 2007

ISBN 2-910239-68-3, Ed. SFGP, Paris, France

interconnected mass of biopolymeric matt, instead of clearly isolated, individual fibers like in the native
kraft pulp.
Differential scanning calorimetry (DSC) was utilized to investigate of the properties of recovered
materials. According to the curves obtained for native cotton linter (Fig.5 a.), cotton linter recovered from

[Amim][Cl] (Fig.5 b.) and cotton linter (CL) recovered from [Bmim][Cl] (Fig.5 c.), the gelling point
changes from 73.43C (native cotton linter) to 77.15C (recovered from [Amim][Cl]) and to 91.78C
(recovered from [Bmim][Cl]), respectively. Initiation temperature of gelling for the materials is similar in
all samples: 40.27C, 40.90C and 42.80C for initial CL, recovered from [Amim][Cl] and [Bmim][Cl],
respectively. Hence, this is circumstantial evidence for the process of non-derivatizing dissolution of
cellulose upon which the degree of polymerization does not change significantly. Otherwise the initiation
temperature of gelling for recovered samples should have been changed dramatically, too. Likewise, it
can be observed that on images for recovered materials, a characteristic peak of crystallization process
appears. The starting sample of cotton linter has no apparent crystallization area due to its initial
crystallinity. The appearance of such a peak on the images of recovered samples is an evidence that the
initial crystallinity has been lost during the dissolution process and further regeneration. The recovered
samples from [Amim][Cl] and [Bmim][Cl] have the crystallization initiation points at 265.51C and

6-9

Rcents Progrs en Gnie des Procds, Numro 94 - 2007

ISBN 2-910239-68-3, Ed. SFGP, Paris, France

244.47C, respectively. The enthalpies of crystallization observed were 58.40 J/g for CL recovered from
[Amim][Cl] and 76.01 J/g for CL recovered from [Bmim][Cl],.the enthalpies of gelling being 105.7 J/g
and 138.7 J/g for CL recovered from [Amim][Cl] and [Bmim][Cl], respectively.

Figure 5. DSC scans for fresh cotton linter (a), cotton linter recovered from [AMIM][Cl] (b) and cotton linter
revovered from [BMIM][Cl (c).]

Essential information concerning compositions of the samples can be obtained from thermogravimetric
analysis (TGA). All the recovered samples demonstrated low decomposition temperature and lower loss

7-9

Rcents Progrs en Gnie des Procds, Numro 94 - 2007

ISBN 2-910239-68-3, Ed. SFGP, Paris, France

100

of the weight, in comparison to

native cotton linter. The native
material
has
decomposition
temperature in the range of 315410C while the recovered samples
undergo degradation at 260 to
300C. Native cotton linter suffers
from a weight loss of ~30% whilst
the recovered samples are subject to
lower weight loss during pyrolysis,
resulting into a weight loss of ~13%
(Fig. 6.). It is of importance to
mention that similar kind of TGA
behavior was also observed by
Swatloski et al. in the 15, indicating
a good orrelation with our results. It
is suprising that the ionic liquids
demonstrated a similar correlation

CL reg from AMIMCl

weight, %

90
CL reg BMIMCl

80

CL initial

70
0

100

200
300
temperature, C

400

Figure 6. TGA of cotton linter (CL); from bottom-up: native CL, CL

recovered from [Amim][Cl] and CL recovered from [Bmim][Cl]
ionic liquids.

90

90

80

80

70

70

60
AMIMCl (reg.)
50
40

w eig ht, %

100

w eight, %

100

60

BMIMCl (reg.)

50
40

AMIMCl (after US 10 min)

30

30
AMIMCl (initial)

20

20
10

10

BMIMCl (initial)

0
0

50

100

150

200

250

temperature, C

300

350

400

450

50

100

150

200

250

300

350

400

temperature, C

Figure 7. TGA of native [Amim][Cl], sonicated and recovered ionic liquid after celllulose dissolution
(left). TGA of native [Bmim][Cl] and recovered ionic liquids after cellulose dissolution (right).

in terms of the sample weight loss (Fig. 7). Regenerated [Amim][Cl] displayed less prominent weight loss
in comparison to native sample. Also, interestingly [Amim][Cl] exposed to sonication for 10 min
demonstrated a lower weight loss than the native liquid, although all three samples have an identical
decomposition temperature close to 273C. In the case of [Bmim][Cl], the behaviour is similar as in the
case of cotton linter and [Amim][Cl] samples, but regenerated [Bmim][Cl] displays a lower
decomposition temperature than native sample.

5. Conclusions
The possibility of high-intensive ultrasound utilization in the process of cellulose processing in ionic
liquids was successfully studied. It was found that an ultrasound treatment allows one to enhance the
dissolution process profoundly being non-derivatizing method at the same time. Manifold physicochemical methods such as acid methanolysis, TGA, DSC, SEM as well as NMR on nuclei 1H and 13C
were applied to investigate the structure and morphology of the cellulose samples series before and after
processing in the ionic liquids. The properties of utilized ionic liquids were also monitored by the means

8-9

450

Rcents Progrs en Gnie des Procds, Numro 94 - 2007

ISBN 2-910239-68-3, Ed. SFGP, Paris, France

of NMR spectroscopy and TGA analysis revealing no degradation or any contamination of the samples
during the process of the cellulose dissolution. Both the cellulose sample and the corresponding ionic
liquid can be easily recovered and reused.
References
Dawsey, T.R., McCormick, C.L., J., 1990, Macromol. Sci., Reviews in Macromolecular Chemistry and Physics
C30(3-4), 405-440
Dorn, S. and Heinze, T., 2006, Center of Excellence for Polysaccharide Research, Friedrich Schiller University of
Jena, Proc. of the 1st International IUPAC conference on Green-Sustainable Chemistry, Sept. 10-15, Dresden,
Germany
Edgar, K.J., Arnold, K.M., Blount, W.W., Lawniczak, J.E.; Lowman, D.W., 1995, Macromolecules 28, 4122-4128
Fischer, S., Voigt, W., Fischer, K.,1999, Cellulose 6, 213-219
Hattori, K., Cuculo, J.A., Hudson, S.M., 2002, J. Polym. Sci. Part A: Polym. Chem. 40, 601-611
Heinze, T., Liebert, T., 2001, Prog.Polym.Sci. 26, 1689-1762
Huddleston, J. G.; Visser, A. E.; Reichert, W. M.; Willauer, H. D.; Broker, G. A.; Rogers, R. D., 2001, Green. Chem.
3, 156-164Tamai, N., Tatsumi, D., Matsumoto, T., 2004, Biomacromolecules, 5, 422-432
Kwon, I.-H., Choi, S.-M., Lee, T.-J., 2006 U.S. Pat. Appl. Publ., Application: US 2005-47683 20050202
Leng, W. and Mormann, W., 2006, Lab. Fr Makromolekulare Chemie, Universitt Siegen, Proc. of the 1st
International IUPAC conference on Green-Sustainable Chemistry, Sept. 10-15, Dresden, Germany
Masson, J.-F., Manley, R.S.J., a.1991, Macromolecules 24, 5914-5921
Masson, J.-F., Manley, R.S.J., b.1991, Macromolecules 24, 6670-6679
Nishino, T., Matsuda, I., Hirao, K., 2004, Macromolecules 37, 7683-7687
Nishio, Y., Manley, R.S., 1988, Macromolecules 23, 849-859
Swatloski, R. P.; Spear, S. K.; Holbrey, J. D.; Rogers, R. D., 2002, J. Am. Chem. Soc. 124, 4974-4975.
Terbojevich, M., Cosani, A., Conio, G., Ciferri, A., Bianchi, E., 1985, Macromolecules 18, 640-646
Zhang, H; Jin, W.; Jiasong, H., 2005 Macromolecules 38, 8282-8287.

Acknowledgments
The financial support from the Academy of Finland is gratefully acknowledged (Decisions nr. 209391
and 211463). This work is part of the activities at the bo Akademi Process Chemistry Centre (PCC)
within the Finnish Centre of Excellence Programmes (2000 2005 and 2006 - 2011) by the Academy of
Finland. Moreover, the authors gratefully acknowledge M.Sc. Clifford Ekholm for SEM analysis.

9-9