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The main goal of our research deals with a new greener and more ecient lignin modication method to
optimize its structural performance as a phenol-formaldehyde resin ller. Through the appropriate increase
in the phenolic hydroxyl content, added value as a raw material was intended. For that, a series of mixtures
of zinc chlorideurea with dierent molar ratios was prepared to obtain deep-eutectic solvents (DESs). Two
heating methods (oil bath and microwave heating) were compared and optimized. Microwave helps in
reducing the preparation time but to the detriment of temperature control. On the other hand, heating
with an oil bath provided better temperature control and homogeneity of the mixture. The preferable
molar ratio of ZnCl2urea was 3 : 10 (Tg 26.3 C). The structural changes of the pretreated lignin
samples were investigated by Fourier transformed infrared and X-ray photoelectron spectroscopies,
scanning electron microscopy, induced coupled plasma and X-ray diraction. Thermogravimetric
analysis demonstrated signicant dierences in the thermal behavior of the recovered lignin as a result
of DES treatment. The weight of lignin recovered was 4 times that of original lignin, indicating that the
structure of lignin was transformed through the integration of Zn. The integration of Zn enhanced the
thermal stability and enhanced lignin's reactivity towards phenol-formaldehyde resin formation. Phenol-
Received 19th December 2014
Accepted 18th March 2015
formaldehyde resin containing the recovered lignin exhibited lower thermocuring temperatures and
better thermostability than those without ller. To the best of our knowledge, this is the rst report on
DOI: 10.1039/c4ra16734a
the investigation of the structural transformations of lignin through its dissolution in ureaZnCl2 DES and
www.rsc.org/advances subsequent use as ller for phenol formaldehyde resin synthesis.
28778 | RSC Adv., 2015, 5, 2877828785 This journal is The Royal Society of Chemistry 2015
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more components that are capable of self-association through purication. Lignin was purchased from ALM India Protobind
hydrogen bonding to form a mixture with a melting point lower 2400 and was dried for 5 h at 60 C. The moisture content of
than that of each individual component.6 DESs are usually lignin was 2.56%. The PF resin with 45.6% solids and viscosity
liquids at temperatures lower than 100 C. Although DESs of 116 mPa s was obtained from Dynea Nanjing.
exhibit almost identical physicochemical properties to tradi-
tional ionic liquids, they do oer advantages due to their lower Preparation of DES
cost and environmentally friendlier nature.7 Besides, the purity
Zinc chloride and urea were mixed in dierent proportions and
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SEM analysis Sunshine gel time (SGT) of PF resin short wire method
Scanning electron microscopy (SEM) was used to provide SGT test is based on a method obtained from Ralph Wilson
information on the particle size and the surface of lignin and Plastics, formerly known as PTM-5. Briey, 6.1 g of sample
relignin. The model of the SEM is FEI Quanta 200. Samples were including PF resin, lignin with PF resin (LPF), and relignin with
gold-coated prior analysis. PF resin (RLPF), respectively, were placed in an 18 150 mm
test tube (without catalyst). The tube was placed in an oil bath
and the time for the resin to gel was determined at 130 0.5 C.
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XPS analysis
XPS spectra were obtained with a Kratos Axis 165 XPS/AES,
operated with a Monochromatic Al Ka (1486.6 eV) source with Results and discussion
an emission current of 10 mA at 15 kV. Samples were loaded Preparation of DES
with double-sided carbon tape. A thin layer of powder was
In order to investigate the optimal parameters for DES forma-
applied to one side of the carbon tape, which was attached to
tion, various zinc chloride to urea mole ratios were tested. The
the sample-loading bar. Samples were analyzed in a high
criteria included the time for the DES's formation, maximum
vacuum chamber with a pressure of 6 109 Pa. A quick survey
temperature during the process, formation of homogenous
scan at the pass energy of 40 eV and high resolution elemental
liquid and lifetime of the liquid. Two types of heating were also
scans at pass energy of 160 eV were performed on each sample.
tested; namely, microwave irradiation and oil bath heating. The
The elemental scans were used to quantitatively analyze the
results are shown in Table 1 and 2. With microwave irradiation,
composition of the samples.
the reaction rate can be increased, but only to the detriment of
temperature control and reproducibility. In addition, DESs tend
to crystallize aer a few days implying the formation of meta-
XRD and ICP-MS analysis stable mixtures (Fig. 1).
X-ray diraction for powder was performed in relignin and The time at which the rst solid crystal within the liquid was
lignin in a Panalytical Emperyan model with a PIXcel3D observed, was denoted as the storage lifetime. Table 2 and Fig. 2
multipurpose mounting system. Relignin was digested with show some features of mixtures of zinc chloride and urea in
peroxideacid treatment and the product was then dissolved in dierent molar ratios heated in an oil bath. The evolution of
a 2% nitric acid solution and analysed using laser ablation DES formation is directly related with their stability over time,
ICP-MS ICP-Q model with a LSX-213 laser ablation system e.g., as the Zn content is lower than 2.5 : 10 (to urea) the time
through a standard addition method with a 200.8 cal-2 ADH required for the formation of a liquid is considerable longer
Standard (20 mg mL1). than that required for the formation of the liquid consisting of
Molar ratio (ZnCl2urea) Time (s) Temp. ( C) Initial/nal appearance Lifetime (days)
Molar ratio (ZnCl2urea) Time (min) Temp. ( C) Initial/nal appearance Lifetime (days)
28780 | RSC Adv., 2015, 5, 2877828785 This journal is The Royal Society of Chemistry 2015
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Fig. 1 Storage of DES prepared under microwave irradiation after the the type of transition metal ion to which urea coordinates.
second day (left) and after the 7th day (right).
Considering the resonance structure of urea, H2N(C]O)NH2,
there are two functional groups (carbonyl and amino, C]O
and NH2) in its structure capable of forming metalurea
complexes. When the formation of complexes occurs through
oxygen and metal ion, the stretching vibration frequency of
carbonyl shis toward lower wavenumber.
Contrary, when the amino nitrogen is the complexing atom,
the carbonyl stretching vibration frequency shis to higher
wavenumber. MetalO bonding in transition metal salts
(including Zn) with urea has been widely reported in literature.24
Fig. 2 Appearance of DESs prepared by heating in an oil bath.
The coexistence of ZnOC]N and ZnO]CN resonance
structures are possible, therefore the interaction of carbonyl in
3 : 10 (ZnCl2urea). Below 2.5 : 10 it is not possible to obtain a urea with Zn is responsible for the red shi of carbonyl in DES
homogeneous liquid, and instead white crystals remain on top spectrum, where the majority of the carbonyl oxygen atoms in
of the liquid formed. On the other hand, as Zn content was urea participate in forming coordination complexes.
further increased above 4 : 10 (to urea) the mixture becomes The strong interaction between oxygen in the carbonyl group
again heterogeneous, the preparation time increases and the of urea and zinc weaken the Coulombic attraction between Zn2+
lifetime of the mixture is reduced signicantly. and Cl by increasing the size of the zinc cation and thus
lowering the melting point of the mixture to nally result in a
ATR-FTIR spectroscopy eutectic liquid at room temperature. This is in agreement with
The FTIR spectrum of DES provided useful information the view of Dishun Zhao et al.25 that urea, as a ligand, forms
regarding intramolecular interactions between the DES's coordination compounds with metal salts, specically with
components. Four mixtures of zinc chloride and urea with ZnCl2. They propose that ZnCl2urea form a stable coordination
dierent mole ratios were tested (Fig. 3). compound with formula Zn[OC(NH2)2]3Cl2, composed entirely of
All of them showed similar spectra, however some dier- a Zn2+ cation coordinated with three oxygen from urea and two
ences are noticeable. chlorine anions. During the reviewing process of this paper
For instance, the shoulder around 3200 cm1 increases its Zhang and colleagues26 reported that [n(urea)/m(ZnCl2)] deep-
intensity as the relative amount of urea increases, indicating an eutectic solvents, with n 1, 2, 3, 4 and m 1, resulted in
increase of the NH bonds. Also the shoulder next to the energy minimum structures through DFT calculations, in
contrast when the number of urea molecules rise to 5 and above,
thus supporting the experimental ndings presented here.
Fig. 3 (A) ATR FTIR of DESs varying the ratio ZnCl2urea. (B) ATR FTIR Fig. 4 (A) DSC of DES varying the ratio ZnCl2urea. (B) TG-DTG of
of ureaZnCl2 3 : 10 and its constituents. ZnCl2urea 3 : 10.
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28782 | RSC Adv., 2015, 5, 2877828785 This journal is The Royal Society of Chemistry 2015
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Zn 2p 0 10.3 0 35.22
O 1s 18.97 27.58 23.79 23.08
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XPS analysis
Oxygen, carbon and a very small amount of nitrogen were
observed on the surface of pristine lignin. On the other hand
relignin exhibited oxygen and a little less carbon content than
Fig. 8 SEM images of lignin (A), relignin (B) and (C) is an enlargement
of the region in the red circle in (B). Fig. 9 XPS spectra of lignin and relignin.
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28784 | RSC Adv., 2015, 5, 2877828785 This journal is The Royal Society of Chemistry 2015
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