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Deep eutectic solvents as highly active catalysts

Cite this: Green Chem., 2015, 17,
for the fast and mild glycolysis of poly(ethylene
Published on 23 January 2015. Downloaded by Fudan University on 19/04/2018 18:36:01.

2473 terephthalate)(PET)†
Qian Wang,a,b Xiaoqian Yao,a Yanrong Geng,a Qing Zhou,a Xingmei Lu*a and
Suojiang Zhang*a

Received 5th December 2014,
Accepted 23rd January 2015
DOI: 10.1039/c4gc02401j
www.rsc.org/greenchem
Deep eutectic solvents (DESs) have attracted broad attention due to their low cost, easy preparation, low
toxicity, good biological compatibility and similar characteristics to those of ionic liquids (ILs). In this study,
we found that not only the glycolysis time is sharply shortened under mild reaction conditions, but also
the high selectivity of monomer bis(hydroxyalkyl) terephthalate (BHET) is obtained when DESs were used
as catalysts. Then, the influences of technological parameters on PET degradation were investigated and
the optimization conditions were obtained. Under the optimization conditions of ethylene glycol (EG)
(20 g), catalyst (n(urea)/n(ZnCl2) 4/1, 0.25 g), PET (5 g), and atmospheric pressure at 170 °C for 30 min, the
conversion of PET and selectivity of BHET were 100% and 83%, respectively. This time is equal to that
taken by a supercritical method under 15.3 MPa at 450 °C. In addition, the degradation mechanism of PET
wastes catalyzed by DESs is proposed through the experiments and DFT calculations. The high catalytic
activity is attributed to the synergetic catalysis of H-bonds and coordination bonds formed between the
DES catalyst and EG.

1 Introduction
The annual world consumption of poly(ethylene terephthalate)-
(PET) has exceeded 50 million tons and is still increasing
markedly due to its widespread use in the fields of bottles,
packaging and fibers.1–3 With such a tremendous consump-
tion, the waste emissions of PET has caused serious “white
pollution” and resource waste. Effectively recycling PET wastes
has become a global problem, which must be urgently solved
for environmental protection and resource preservation.
The chemical recycling method, as a promising method,
was studied by many scientists and many great results were
achieved, such as high conversion and reproducing the virgin
plastic products from the obtained original feedstock mono-
mers, but there are still some drawbacks such as slow reaction
rate, low selectivity and severe reaction conditions. These draw-
backs result in high cost and high energy consumption of the
a
Beijing Key Laboratory of Ionic Liquids Clean Process, Key Laboratory of Green
Process and Engineering, Institute of Process Engineering, Chinese Academy of
Sciences, Beijing 100190, PR China. E-mail: xmlu@ipe.ac.cn, sjzhang@ipe.ac.cn;
Fax: +86 10 8262 7080
b
College of Chemistry, Chemical Engineering and Materials Science,
Shandong Normal University, Jinan, Shandong 250014, PR China
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c4gc02401j
PET degradation process, which is not conducive for the indus-
trial processing of recycling of PET wastes. To overcome these
drawbacks, researchers have been mainly devoted to employ
different catalytic systems,4–6 develop microwave-assisted tech-
nology7,8 and explore a supercritical method.9–13 Catalysts,
including acids,14 metal salts15,16 and bases,17 have already
been widely investigated with some advantages in PET recy-
cling, such as high PET conversion and obtaining original
feedstock monomers, while there are also some drawbacks
such as slow reaction rate, low selectivity and severe reaction
conditions. Microwave-assisted technology can enhance the
reaction rate, but high power, high pressure and high tempera-
ture are usually needed. The supercritical method can attain a
high degradation rate of PET, but the reaction conditions are
more severe (300–450 °C, 14–50 MPa).10,11 For example, the
reaction time can be greatly shortened to 30 min in supercriti-
cal ethylene glycol (EG), but it was possible under 15.3 MPa at
450 °C.11 Therefore, the study on PET degradation with high
selectivity and fast reaction rate under mild conditions is still
the most desirable and important work to accelerate the indus-
trial recycle process of PET wastes.
It has been reported that the synergetic effect of catalysts
can speed up a chemical reaction, make the reaction con-
ditions milder and also improve the selectivity of product.18–21
Yamamoto et al. found that the combination of organic and in-
organic molecules bearing acidic groups could result in higher

This journal is © The Royal Society of Chemistry 2015 Green Chem., 2015, 17, 2473–2479 | 2473

Paper
catalytic activity than individual catalysts for acid-catalyzed
reactions.20 Wang et al. and Zhou et al. found that the syner-
getic effect of cations and anions of the ionic liquid catalyst
could make the degradation conditions of PET milder.22–24
Our previous work indicated that urea, as a green, cheap, re-
usable catalyst, shows a high catalytic activity in the glycolysis
of PET wastes under mild reaction condition. H-bonds formed
between urea and EG were proved to play a key role in the
degradation process by in situ IR, DFT calculation and experi-
ments, and the synergetic effect of cations and anions of the
amino acid-functionalized ionic liquid catalyst by H-bond can
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accelerate the degradation of PET.25 Considering that the
coordination bond of metal salt are usually stronger than
H-bond, we infer that combining H-bond and coordination bond
might greatly improve catalytic activity and accelerate reaction
rate.
Deep eutectic solvents (DESs), as an alternative to ionic
liquids (ILs), not only have similar characteristics to those of
ILs, but are also cheaper to produce (lower cost of the raw
materials), less toxic, and often biodegradable.26,27 Because of
these properties, they have been applied in many fields such
as biocatalysis, extraction, carbon dioxide capture, biomedical
applications and material synthesis.28,29 However, their appli-
cation in the PET degradation as catalysts has not been
reported. Even more important, DESs synthesized by urea and
metal salts can have both strong H-bond action and coordi-
nation action. Moreover, upon addition of a small amount of
metal salt into urea catalyst, the catalytic activity was greatly
improved. Therefore, in this work, a series of new urea/metal
salt DESs with various cations or anions of metal salts were
prepared and were used for the PET degradation reaction as
catalysts. The structure and purity of the product were ana-
lyzed by gas chromatography-mass spectrometry (GC-MS) and
nuclear magnetic resonance spectroscopy (NMR). The influ-
ences of experimental conditions on the degradation efficiency
of PET were investigated. Finally, the degradation mechanism
of PET wastes catalyzed by DESs was studied by the experi-
ments and density functional theory (DFT) calculations.
2 Experimental section
2.1 Materials
PET pellets were purchased from Jindong Commercial Co. Ltd,
Jiangsu Province, China. Their viscosity-average molecular
weight was 2.63 × 104 g mol−1, which was tested using ASTM D
4603. Zinc chloride (ZnCl2) was supplied by Alfa Aesar, A
Johnson Matthey Company. Urea, zinc acetate (ZnAc2·2H2O),
manganese acetate (MnAc2·4H2O), cobalt acetate
(CoAc2·4H2O), manganese chloride (MnCl2·2H2O) zinc sul-
phate (ZnSO4·7H2O), zinc nitrate (Zn(NO3)2·6H2O), copper
acetate (CuAc2·H2O), EG, phenol and 1,1,2,2-tetrachloroethane
(99% purity) were obtained from Sinopharm Chemical
Reagent Beijing Co., Ltd, China. The materials were used
without any further treatment.
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2.2 Preparation of DESs
A series of urea/metal salt mixtures were synthesized by
mixing urea with metal salts at molar ratios of urea to
metal chloride from 12 : 1 to 6 : 1 at 70–100 °C for 2–6 h until
clear, transparent, homogeneous target liquids appeared.
2.3 Characterizations of catalysts and main products
FT-IR spectra of the urea-based mixtures were obtained using
a Nicolet 380 (Thermo Fisher Scientific, USA) spectrometer.
The structure of the main product was analyzed by NMR
(ECA-600, JEOL, Japan) in d6-DMSO solution and GC-MS spec-
trum, which was collected using a 6890N Network GC System
and a 5975B inert MSD (Agilent, USA).
2.4 General procedure for the catalytic degradation
of PET
5 g of PET pellets were degraded, in each experiment, using
EG in the presence of the synthesized catalyst. A three-necked
round-bottom 50 mL glass flask equipped with a thermometer,
a reflux condenser and a magnetic stirrer was used for all the
glycolysis experiments. The degradation reactions were carried
out under atmospheric pressure at 170 °C for reaction times of
10 min–60 min. The flask was immersed in an oil bath at a
specific temperature for the required time. When the reaction
was completed, the reaction mixture was cooled to room tempe-
rature. Then, an excess amount of distilled water was added
to separate the residual PET pellets from the products. The
residual PET was dried at 70 °C to constant weight and
weighed to calculate the conversion of PET, which is defined
by the following equation:
Conversion of PET ¼
initial weight of PET  weight of residual PET
 100%
initial weight of PET
Moreover, the degradation products were separated
according to the separation methods from the literature.23–25
The degradation products were vigorously agitated after
adding about 900 mL of cold distilled water and then filtered
(the main product, excess of EG and catalyst would be dis-
solved in the distilled water). The collected filtrate was con-
centrated to about 60 mL using a vacuum rotary evaporator at
50 °C. The concentrated filtrate was stored in a refrigerator at
0 °C for 12 h. White needle-like crystals were formed in the
filtrate, which were then filtered and dried. GC-MS and NMR
characterizations (see Fig. S1 and S2 in ESI†) show that these
crystals are bis(hydroxyalkyl) terephthalate (BHET) monomer
with high purity (1H NMR: δ ( ppm) = 8.08, 4.93, 4.29, 3.69;
13
C NMR: δ ( ppm) = 165.68, 134.26, 130.03, 67.55, 59.52).
The selectivity of BHET is calculated by the following
equation:
moles of BHET
Selectivity of BHET ¼
moles of depolymerized PET units
 100%
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2.5 Method of structure optimizations

All the DFT calculations were carried out using the Gaussian
03 program. The B3LYP/6-311++G (d,p) method has been used
for structure optimizations, and the subsequent frequency cal-
culations at the same level verify the optimized structures to
be at ground states without imaginary frequencies (NImag = 0).
All the possible coordination numbers were considered includ-
ing 1, 2, 3, 4, 5, and 6.

3 Results and discussion

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3.1 Synthesis and characterizations of DESs

The prepared urea/metal salt mixtures were characterized by
FT-IR, and some of their spectra are shown in Fig. 1. It can be
seen that the new peaks at 2220.50, 2191.30 and 2223.15 cm−1
appeared compared with the FT-IR spectrum of urea, which
indicated that new bonds were formed by the coordination
between urea and metal salts.30,31 Moreover, the vibrations for
carbonyl in urea showed obvious red shifts from 1681.02 to
1658.72 cm−1 and from 1584.59 to 1645.91 cm−1, which
showed that the coordination bonds were mainly formed
between oxygen of carbonyl in urea and metal ion.30,31 Then,
the structures of urea/ZnCl2 were optimized by B3LYP/6-
311++G(d,p) method and some relatively stable structures are
shown in Fig. S3–S6 in ESI.† It was found that there are
different energy minimum structures for the coordination
between ZnCl2 and urea when the coordination numbers were
1, 2, 3, and 4. However, the structures with coordination
numbers of 5 and 6 could not be found. Moreover, the coordi-
nation bonds were mainly formed between Zn2+ and oxygen of
carbonyl in urea, which is consistent with FT-IR results.
3.2 Freezing point curves of DESs
The freezing point curves of three synthesized mixtures with
different mole ratios of components were tested and are
shown in Fig. 2. Compared with the urea and metal salts, the
freezing points of the mixtures decreased. The freezing points
Fig. 2 Freezing point curves of the synthesized urea/metal salt mix-
tures with some digital images (inset) of the synthesized DESs.
of some mixtures are below 100 °C. Parts of these mixtures
even present liquid at room temperature due to their freezing
points below 10 °C, such as urea/MnAc2·4H2O from 4/1 to 1/1
of n(urea)/n(MnAc2·4H2O), and urea/ZnAc2·2H2O from 4/1 to 1/1
of n(urea)/n(ZnAc2·2H2O). Some DESs with low freezing points
are also shown in the images a–c in Fig. 2. The lower freezing
points are mainly attributed to the coordination between the
metal ion and urea, which weaken the coulombic force
between cations and anions of the metal salt and sequentially
decrease the freezing points of the mixtures.
3.3 Test of catalytic activity
The catalytic activities of the synthesized DESs were then eval-
uated and the results are shown in Fig. 3. It can been seen that
the DESs with mole ratios between 6/1 and 4/1 showed high
catalytic activities. Not only the reaction time becomes shorter,
but also the selectivity of BHET is higher than that with the
other mole ratios of mixtures. The reaction time is only 30 min
under atmospheric pressure at 170 °C, which is far shorter
than that when catalyzed by urea,25 metal salts15,16 and the
other catalysts, such as solid super acids,14 metallic oxides6

Fig. 3 Effect of different mole ratios of urea and metal salt on the
degradation of PET. Reaction conditions: PET (5.0 g), EG (20 g), catalyst
Fig. 1 IR spectra of the synthesized urea-based DESs. (0.25 g), atmospheric pressure at 170 °C, conversion of PET (100%).

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Table 1 Comparison of reaction conditions and catalytic activities of PET degradation

Temperature/ Pressure/ Time/ PET BHET

Source Catalyst Solvent °C MPa min conversion/% selectivity/%

This work Urea/ZnCl2 DES EG 170 0.1 30 100 82.80

Urea/ZnAc2·2H2O DES EG 170 0.1 30 100 81.14
Urea/MnAc2·4H2O DES EG 170 0.1 30 100 80.05
Urea EG 170 0.1 210 100 68.9
ZnCl2 EG 170 0.1 120 100 71.39
ZnAc2·2H2O EG 170 0.1 140 100 70.06
MnAc2·4H2O EG 170 0.1 140 100 71.39
Ref. 14 SO4/ZnO-TiO2 EG 180 0.1 180 100 72
Ref. 6 γ-Fe2O3 EG 255 >0.1 80 — >80
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Ref. 15 ZnAc2 EG 197 0.1 90 98.66 —

Ref. 16 MnAc2 EG 190 0.1 120 99.96 —
Ref. 22 [Bmim][H2PO4] EG 175 0.1 480 6.9 —
[Bmim][HSO4] EG 170 0.1 480 0.5 —
[3a-C3P(C4)3][Gly] EG 180 0.1 480 100 —
[3a-C3P(C4)3][Ala] EG 180 0.1 480 100 —
[Bmim]Cl EG 180 0.1 480 44.7 —
[Bmim]Br EG 180 0.1 480 98.7 —
Ref. 23 [Bmim][FeCl4] EG 178 0.1 240 100 59.2
Ref. 24 [Deim][Zn(OAc)3] EG 180 0.1 90 100 67.10
[Deim][Cu(OAc)3] EG 180 0.1 120 100 58.64
[Deim][Mn(OAc)3] EG 180 0.1 225 100 51.30
[Deim][Co(OAc)3] EG 180 0.1 150 100 56.65
[Deim][Ni(OAc)3] EG 180 0.1 105 100 54.13
Ref. 25 Urea EG 180 0.1 150 100 73.05
Ref. 11 — Supercritical EG 450 15.3 30 100 —
Ref. 10 — Supercritical methanol 300 14.7 30 near 100 —

and ionic liquids,22–24 and is even comparable with that by a

supercritical method such as using supercritical EG under
15.3 MPa at 450 °C and supercritical methyl under 14.7 MPa at
300 °C.10,11 Obviously, the reaction conditions of this method
are considerably milder than that of a supercritical method.
This method is more energy-efficient. Moreover, the selectivity
of this method reaches up to 83%, which is also higher than
that catalyzed by the other catalysts.14,22–25 The detailed com-
parison results of degradation conditions and catalytic activi-
ties are shown in Table 1. Therefore, this type of catalysts
indicate a promising industrial prospect in the efficient recy-
cling of PET wastes due to their low cost, easy preparation,
high activities and relatively mild degradation conditions.
Moreover, Fig. 3 also shows that the reaction time becomes
Fig. 4 Effect of the amount of catalyst on the degradation of PET.
longer with the mole ratios of urea and metal salts increasing
Reaction conditions: PET (5.0 g), EG (20 g), catalyst (n(urea)/n(ZnCl2)
from 6/1 to 12/1 or decreasing from 4/1 to 1/4, and the reaction 4/1, 0.25 g), atmospheric pressure, 170 °C, 30 min.
time catalyzed by urea/metal salt DESs is obviously shorter
than that when catalyzed by a single catalyst, such as only
urea, ZnCl2, ZnAc·2H2O or MnAc2·4H2O, which indicated that selectivity of BHET has the same trend because the catalyst
the high catalytic activity of urea/metal salt mixtures resulted concentration influences the mass transfer among catalyst, EG
from the synergetic catalysis between urea and metal salts. and PET.
Fig. 5 shows that reaction temperature greatly influences
3.4 Effect of reaction conditions the degradation of PET. The conversion of PET increases with
Some factors influencing the PET degradation were investi- the reaction temperature increasing and reaches 100% when
gated. Fig. 4 presents the effect of the catalyst amount on the the temperature reaches 170 °C and above. The selectivity of
degradation of PET. When the catalyst was added, the conver- BHET reaches the maximum value (83%) at 170 °C with 100%
sion of PET and selectivity of BHET both increase sharply, con- conversion of PET. The selectivity is higher than that catalyzed
siderably higher than that without catalyst. The conversion of by urea,25 metal acetates,15,16 solid super acids14 and ionic
PET increases with the increasing amount of catalyst from 0 g liquids.22–24 Therefore, DES, as a catalyst, has a good BHET
to 0.25 g, and then it reaches to 100% from 0.25 g to 2.0 g. The selectivity for the glycolysis of PET.

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Fig. 5 Effect of temperature on the PET degradation. Reaction con-
ditions: PET (5.0 g), EG (20 g), catalyst (n(urea)/n(ZnCl2) 4/1, 0.25 g),
atmospheric pressure, 30 min.
Fig. 6 Effect of reaction time on the degradation of PET. Reaction con-
ditions: PET (5.0 g), EG (20 g), catalyst (n(urea)/n(ZnCl2) 4/1, 0.25 g),
atmospheric pressure, 170 °C.
Fig. 6 displays that the conversion of PET increases sharply
up to 100% at 30 min and then remains 100%, and the selecti-
vity of BHET has maximum value at 30 min (83%) with the
increasing of reaction time from 10 min to 30 min. This is
because there is an equilibrium reaction between BHET and
the dimer and oligomer.25
Thus, it can be seen that reaction temperature and reaction
time are crucial factors for the degradation of PET and the
optimization conditions were obtained by studying the effects
of reaction conditions. Under the optimization conditions (EG
(20 g), catalyst (n(urea)/n(ZnCl2) 4/1, 0.25 g), PET (5 g), atmos-
pheric pressure at 170 °C for 30 min), the conversion of PET
and selectivity of BHET are 100% and 82.80%, respectively.
3.5 Glycolysis mechanism of PET
To find the synergetic catalysis between urea and metal salts,
another five urea/metal salt DESs were synthesized and were
used in the catalytic degradation of PET. The results, with the
other three catalysts mentioned above together, are summar-
ized in Table 2. It can be seen that most of these mixtures
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Table 2 Comparison of PET degradation with different catalystsa
Time/ Selectivity
Catalyst min of BHET/%
Urea/ZnSO4·7H2O 40 74.72
Urea/Zn(NO3)2·6H2O 30 78.31
Urea/ZnCl2 30 82.80
Urea/ZnAc2·2H2O 30 80.05
Urea/CoAc2·4H2O 30 81.53
Urea/CuAc2·H2O 50 79.28
Urea/NiAc2·4H2O 120 70.37
Urea/MnAc2·4H2O 30 81.14
a
Reaction conditions: PET (5.0 g), EG (20 g), catalyst (n(urea)/n(metal
salts) 4/1, 0.25 g), atmospheric pressure at 170 °C, conversion of PET
(100%).
showed a fast reaction rate. When the cation of metal salts is
Zn2+, the different anions of metal salts have no significant
effect on the degradation rate of PET. However, when the
anion of metal salts is Ac−, the different cations of metal salts
have a great influence on the degradation rate. For example,
the degradation time is 120 min catalyzed by urea/NiAc2·4H2O,
which is longer than the other mixture catalysts. These obser-
vations indicated that the metal ions greatly affected the PET
degradation.
Taking [Zn(urea)]Cl2 as an example, the roles among the
catalyst, EG and PET, were then studied and some possible
stable interaction structures are shown in Fig. 7. It can be seen
that the energetic differences among them are very close,
which indicate the possible free conversion and the equili-
brium among these structures. Moreover, the interaction
among the catalyst, EG and PET is mainly formed by H-bonds
and coordination bonds. The H-bonds were formed between
hydrogen of hydroxyl in EG and oxygen of carbonyl in urea,
between hydrogen of amidogen in urea and oxygen of ester
group in PET, between hydrogen of hydroxyl in EG and oxygen
of ester group in PET, and between hydrogen of amidogen in
urea and oxygen of hydroxyl in EG. Thus, the DESs have more
catalytic active sites than the conventional ionic liquids and
metal salts because they can form more types of H-bonds
between catalysts and PET. Furthermore, the coordination
bonds were also formed between Zn2+ and oxygen of hydroxyl
in EG, which can activate the hydroxyl in EG to enhance the
glycolysis of PET. Therefore, these calculation results demon-
strated that H-bonds and coordination bonds are indeed
formed in the PET glycolysis process and explained with
experiments together. The high catalytic activity of the DESs
resulted from the synergetic interactions between H-bond
interaction of urea and coordination interaction of metal ions.
Based on the experiments and DFT calculations, the poss-
ible degradation mechanism of PET wastes catalyzed by DESs
is illustrated in Fig. 8. It can be seen that the high catalytic
activity is attributed to the synergetic catalysis of H-bonds
formed between urea and EG and coordination bonds formed
between metal ions and EG. First, the H-bonds are formed
between the hydrogen of hydroxyl in EG and the oxygen of
carbonyl in urea. The formed H-bonds make the length of the
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Fig. 7 Optimized interaction structures among catalyst, EG and PET by
B3LYP/6-311++G(d,p) with relative energies. Red: O; green: Cl; blue: N;
white: H; dark grey: C; light gray: Zn.
Fig. 8 Mechanism of the degradation of PET catalyzed by urea/ZnCl2
DES.
O–H bond of hydroxyl in EG longer and the electronegativity of
the oxygen of hydroxyls in EG stronger. These make the hydro-
gen to be lost more easily, let the nucleophilicity of the oxygen
stronger, and finally facilitate the attack of oxygen on the
carbon of the ester group in PET.25 At the same time, the
coordination bonds can be formed between Zn2+ and oxygen
in PET. Thus, relative to the disordered fracture catalyzed by
2478 | Green Chem., 2015, 17, 2473–2479
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conventional catalysts,32 a ring transition state can be formed
among PET, EG and DES catalyst, which regularly fractures the
long chain of PET to accelerate the degradation rate and
enhance the selectivity of PET.
4 Conclusions
In conclusion, urea/metal salt DESs can more effectively cata-
lyze the glycolysis of PET into a monomer with the high con-
version of PET and high selectivity of monomer in a shorter
reaction time under mild conditions. This type of catalysts
show a promising industrial prospect for the efficient recycling
of PET wastes due to their easy preparation, low cost, high
activities and relatively mild degradation conditions. The
optimization conditions were obtained by investigating the
influences of technological parameters on PET degradation.
The study of the degradation mechanism showed that the
higher catalytic activity is attributed to the synergetic catalysis
between H-bonds and coordination bonds formed between
DES catalyst and EG. The results can provide an important gui-
dance for the design of effective catalysts used to promote the
degradation reaction of polymer wastes and other chemical
reactions.
Acknowledgements
This work was supported financially by the Program of
National High Technology Research and Development
Program of China (no. 2012AA063001), the National Natural
Science Foundation of China (no. 21276255, no. 21476234),
Shandong Province Natural Science Foundation (no.
ZR2014BQ018) and the Beijing Natural Science Foundation of
China (no. 2131005, no. 2132055).
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