Wood Sci Technol

DOI 10.1007/s00226-016-0847-8

ORIGINAL

Synthesis and characterization of kraft

lignin-graft-polylactide copolymers

Seok Ju Kim1 • Yong Sik Kim1 • Oh-Kyu Lee1 •

Byoung-Jun Ahn1

Received: 16 September 2015

Ó Springer-Verlag Berlin Heidelberg 2016

Abstract The graft polymerization of polylactic acid (PLA) onto methanol-soluble

kraft lignin (MeKL) was performed successfully through acylation substitution
using chlorine-terminated PLA with a number average of molecular weight (Mn) of
5400–24,000 g/mol. As the Mn value of the PLA used for the graft polymerization
process was increased, the obtained MeKL-g-PLA copolymers decreased from
9,000,000 to 1,100,000 g/mol. The structural characteristics of the MeKL-g-PLA
copolymers were analyzed using Fourier transform infrared and 1H nuclear mag-
netic resonance spectroscopies. It was found that the thermal properties of the
MeKL-g-PLA copolymers improved slightly, with their glass-transition temperature
increasing to a level higher than that of pure PLA. The tensile strengths and elas-
ticity modulus of the MeKL-g-PLA copolymers were independent of the Mn value
and were 3.5–3.8 MPa and 0.038–0.045 GPa, respectively.

Introduction

After cellulose, lignin is the most abundant biopolymer and makes up 15–40 % of
the lignocellulosic biomass, depending on the tree species and the botanical origin
(Fengel and Wegener 1989; Pandey and Kim 2011). It is a class of amorphous and
heterogeneous macromolecules which consist of randomly cross-linked phenyl-
propanoid units (p-coumaryl, coniferyl, and sinapyl alcohol) (Fengel and Wegener
1989; Roberts et al. 2011; Pandey and Kim 2011). It is readily available as a
coproduct of the pulping process. Most of it is primarily burnt as an energy source
and less than 2–5 % of it is used for commercial products (Kadla et al. 2002;

& Yong Sik Kim

yongsikk@korea.kr
1
Division of Wood Chemistry and Microbiology, National Institute of Forest Science,
57 Hoegi-ro, Dongdaemun-gu, Seoul 130-712, Korea

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Kleinert and Barth 2008). However, huge amounts of technical lignin are expected
to be produced as a coproduct if bioethanol production from lignocellulosic biomass
becomes commercially available in the near future. The physical and chemical
properties of lignin vary with the extraction and/or pulping procedure used, which
include alkaline (soda), kraft, sulfite, organosolv, enzymatic, and steam explosion
pulping, among other. This is probably because the structure of the lignin extracted
using the different procedures changes because of the different chemical treatments
used, given the structural complexity of lignin and the various functional groups
(aliphatic and phenolic hydroxyl, methoxyl, carbonyl, and carboxyl groups)
involved. Therefore, it is difficult to produce value-added lignin products (Zakzeski
et al. 2010; Brosse et al. 2011; Doherty et al. 2011). Nevertheless, lignin is
considered a high-potential material, as it is cheap and a renewable and
biodegradable resource.
In recent decades, there has been significant interest in integrating lignin with
currently available synthetic polymers via copolymerization and blending to
develop novel lignin-based biomaterials. The graft copolymerization of hydrophilic
monomers such as acrylamide and vinyl alcohol has been shown to produce
polymers with improved thermosensitive properties as well as hydrogel-type
polymers (Meister et al. 1984; El-Zawawy 2005; Su et al. 2013). The blending of
lignin with synthetic polymers such as polyurethane, polyethylene oxide, polyvinyl
alcohol, polycaprolactone (PCL), polyhydroxybytyrate (PHB), polyglycolide
(PGA), and polylactic acid (PLA) were shown to increase the thermal stability
and processability of lignin (Feldman et al. 2002; Kubo and Kadla 2004;
Pucciariello et al. 2008; Mousavioun et al. 2010; Gordobil et al. 2014; Li et al.
2015). Chung et al. (2013) could directly graft lactic acid onto commercial lignin
catalyzed by triazabicyclodecene, resulting in an improvement in the glass-
transition temperature and ultraviolet absorbance. Moreover, PLA is used widely as
biodegradable and renewable thermoplastic polyester, owing to its excellent
mechanical properties, biocompatible nature, low immunity, and adjustable hy-
drolyzability as well as its potential for replacing petrochemical-based polymers
(Moon et al. 2001; Rasal et al. 2010; Xiao et al. 2010). Accordingly, PLA is
synthesized directly via ring-opening polymerization and/or polycondensation with
or without a catalyst such as tin (II) chloride, tin 2-hexanoate (Sn(Oct)2), and
distannoxane (Moon et al. 2001; Tasaka et al. 2001; Achmad et al. 2009; Xiao et al.
2010).
‘‘Grafting’’ is one of several techniques for modifying the properties of polymers
and involves the covalent bonding of monomers onto the polymer chain. For the
production of lignin-based biomaterials, the grafting method is considered one of
the most effective ways of altering the physical properties (e.g., tensile strength,
thermal stability, etc.) of lignin (Bonini et al. 2003; Bhattacharya and Misra 2004).
Thus, as part of ongoing research into ways to utilize lignin effectively, the graft
copolymerization of PLA onto lignin was investigated in depth. This paper reports
on the synthesis of lignin-based copolymers through acylation by varying the
molecular weight of PLA and the characterization of these lignin-g copolymers in
terms of their thermal and mechanical properties.

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Materials and methods

Materials

All the chemicals used were of analytical grade and were employed as received
from Aldrich and Wako Chemicals. The black liquor was obtained from Moorim
Pulp & Paper Co. (South Korea) and produced by the chemical pulping of a mixture
of various Southeast Asia hardwood chips.

Isolation of kraft lignin (KL) and methanol-soluble kraft lignin (MeKL)

KL was isolated from the black liquor according to the method described by Kim
et al. (2015). The pH of the black liquor was adjusted to approximately 2.0 using
concentrated HCl. The precipitated KL was recovered by filtration, repeatedly
washed with fluent deionized water, and freeze dried in an oven drier at 60 °C for
2 weeks.
MeKL was isolated from KL using the method described by Youe et al. (2016).
The recovered KL was dissolved in an excess amount of methanol at room
temperature and stirred overnight. The insoluble KL was removed by filtration, and
the filtrate was evaporated under reduced pressure to yield dark brown solids. The
recovered solids were dissolved in a small amount of dimethyl sulfoxide (DMSO)
and then added drop wise under stirring to fluent deionized water. The precipitated
MeKL was recovered by filtration through a Nylon membrane (0.45 lm, 47 mm),
washed with fluent deionized water, and dried in an oven drier at 60 °C for 2 weeks.

Synthesis of MeKL-g-PLA copolymers

The MeKL-g-PLA copolymers were synthesized as per Fig. 1. First, 200 g of lactic
acid (LA) was added to a 200 mL flask equipped with a magnetic stirrer and a reflux
condenser connected to a vacuum system through a trap. The LA was dehydrated at
150 °C under reduced pressure for 3 h and was then mixed with 0.4 g of Sn(Oct)2.
The reaction mixture was stirred and heated at 180 °C under reduced pressure for
48 h. Approximately 0.5 mL of the reaction mixture was sampled every 4 h to
determine the molecular weight of the synthetic PLA. At the end of the reaction, the
reaction mixture was cooled to room temperature. The resulting solidified product
was redissolved in 100 mL of dichloromethane (DCM), precipitated in 1.5 L of cold
diethyl ether, filtered, and washed with diethyl ether. The recovered PLA was dried
under reduced pressure to yield a white powder.
The chlorine-terminated PLA (Cl-PLA) was synthesized through acylation. First,
10 g of the dried PLA was dissolved in 20 mL of dry DCM. To this, 20 mL of
thionyl chloride (SOCl2) and 0.1 g of dimethylformamide (DMF) were added. The
mixture was stirred at 60 °C for 4 h in a nitrogen-filled glass reactor. Then, formic
acid was added to the product, which included Cl-PLA, under stirring to remove the
unreacted SOCl2. Finally, the product was evaporated to remove the residual
reagents.

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Fig. 1 Synthesis of the MeKL-g-PLA copolymers

Next, 15 g of MeKL was dissolved in 50 mL of anhydrous pyridine and 10 g of

Cl-PLA was liquefied in 30 mL of anhydrous DCM, and the two solutions were
mixed gradually, while the temperature was maintained at 0 °C using an ice bath.
The mixture was stirred at room temperature for 72 h. At the end of the reaction, the
mixture was precipitated in 1 L of cold water. The precipitates were recovered by
filtration through Whatman No. 6 filter paper (diameter of 110 mm) and washed
with fluent deionized water, methanol, and DCM. Finally, the product, namely the
MeKL-g-PLA copolymers, was dried in an oven drier at 60 °C for 2 weeks, yielding
a brown powder. All the samples were stored in a desiccator until further use.

Characterization

Elemental analyses were performed on 1.5 mg of KL and MeKL at 900 °C using a

Flash EA 1112 series system (Thermo Electron Corporation, Italy). The samples
were oven dried for more than 2 weeks at 60 °C prior to the analyses. All the
analysis samples were subjected to the same pretreatment. The calibration material
used was 2,5-Bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BBOT, Thermo Fischer
Scientific, USA).
The 1H nuclear magnetic resonance (NMR) spectra were obtained using a Bruker
AVANCE 400 MHz spectrometer. Approximately 20 mg of each sample was
dissolved in 0.5 mL of CDCl3 (in case of synthetic PLA) or DMSO-d6 (in case of
MeKL and the MeKL-g-PLA copolymers) and filtered prior to the NMR analysis.
The NMR spectra were recorded at room temperature using a pulse with a width of

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90° and an acquisition time of 1.3 s. A relaxation delay (d1) of 7 s was used to
ensure the complete relaxation of the aldehyde protons. A total of 128 scans were
performed.
Fourier transform infrared spectroscopy (FT-IR) was performed using a
spectrometer (Thermo Fisher Scientific, USA) equipped with an attenuated total
reflectance (ATR) attachment. A total of 128 scans were performed per sample at a
spectral resolution of 4.0 cm-1. FT-IR absorbance spectra were directly obtained
using oven-dried samples.
The molecular weight distributions of MeKL, synthetic PLA, and the MeKL-g-
PLA copolymers were determined using a GPCmax system (Viscotek, USA)
connected to a Dawn Heleos-II multiangle laser light scattering (MALLS) detector
(Wyatt Technology, USA) equipped with fluorescence filter onto the odd number
laser and an Optilab T-rEX refractive index detector (Wyatt Technology, USA). A
series of Agilent PLgel columns (one Mixed-C and two Mixed-D; 300 9 7.5 mm,
5 lm) were used. The synthetic PLA and MeKL samples were analyzed using
tetrahydrofuran as the eluent (0.7 mL/min); the column temperature was kept at
35 °C. The MeKL-g-PLA copolymers were analyzed using a solution of DMF
containing 0.2 M lithium chloride as the eluent (0.7 mL/min); the column
temperature was kept at 70 °C. The sample concentration was 3 mg/mL, and the
injection volume was 100 lm. In addition, the dn/dc values of the MeKL, synthetic
PLA, and MeKL-g-PLA copolymers were determined by Wyatt software (Astra,
version 6.1.2.84) and used for calculating the molecular weight distributions of
them. The dn/dc values of the MeKL, synthetic PLA, and MeKL-g-PLA copolymers
were 0.2483, 0.2084, and 0.1015, respectively.
Differential scanning calorimetry (DSC) was performed using a Q10 DSC system
(TA Instruments, USA) in a flow of nitrogen (50 mL/min). DSC measurements
procedure was as follows: first and second heating with a heating rate of 10 °C/min
from 20 to 170 °C to discard any anterior thermal history, a ramp of 10 °C/min down
to 20 °C, third heating scan from 20 to 170 °C with a heating rate of 10 °C/min. The
sample of approximately 2 mg was used, and the reference was an empty pan.
Thermogravimetric analyses (TGA) were performed using an SDT Q600 system
(TA Instruments, USA) in nitrogen at a heating rate of 10 °C/min between 30 and
600 °C; samples of approximately 3 mg was used.
Specimens of the MeKL-g-PLA copolymers (length of 38 mm 9 width (broad
16 mm, narrow 4.5 mm) 9 depth of 3.0 mm) were produced using a BA-916
injection molding system (Bau Technology, Korea). Tensile tests were performed
on these specimens using a Hounsfield universal testing machine (H50K-S, GB) as
per the ASTM standard D3500 (2009).

Result and discussion

Isolation of methanol-soluble lignin (MeKL)

The KL used in this study constituted 93.1 % Klason lignin content, composed of
87.2 % of insoluble lignin and 5.9 % of acid-soluble lignin according to previous

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studies (Kim and Kim 2013; Kim et al. 2015). However, KL was poorly soluble in
most organic solvent, so MeKL, relatively low molecular weight compared to that
of KL, was isolated from KL in order to increase the solvent solubility for the graft
copolymerization of PLA onto lignin.
Interestingly, compositional analysis of the KL and MeKL revealed that the
sulfur and nitrogen contents of the MeKL were lower than those of KL. This was
probably because sulfur and nitrogen were present in greater amounts in the
methanol-insoluble KL (Table 1). The Mn and polydispersity index (PDI) values of
MeKL were 1600 g/mol and 6.19, respectively, which was over 20 times greater
than MeKL (Mw 654 g/mol) from softwood kraft lignin (Indulin AT) according to
Li and McDonald (2014).

Synthesis of MeKL-g-PLA copolymers

Figure 1 outlines the protocol for synthesizing the MeKL-g-PLA copolymers. The
first step was the polymerization of LA in the presence of Sn(Oct)2. The molecular
size of the synthetic PLA was controlled by varying the reaction time; the molecular
weights of synthetic PLA were determined at fixed time intervals using the GPC-
MALLS system. The substitution of Cl on the end group of synthetic PLA in the
presence of SOCl2 resulted in Cl-PLA in the second step. Finally, the acylation of
MeKL with Cl-PLA yielded the MeKL-g-PLA copolymers. The unreacted MeKL
and Cl-PLA were removed by washing with methanol and DCM, respectively.
Thus, the process was a simple one.
Table 2 lists the Mn values of the MeKL-g-PLA copolymers synthesized
according to the above-described procedure. The molecular weights of the MeKL-g-
PLA copolymers (Mn; 1,100,000–9,000,000 g/mol) were significantly higher than
that of neat MeKL. When the molecular weight of the Cl-PLA samples used for
copolymerization was increased, the size of the MeKL-g-PLA copolymers
decreased, but the final yield of MeKL-g-PLA copolymers was increased from
25.6 to 31.2 g. This was likely because a smaller molecular mass of Cl-PLA could
be more easily grafted either at phenolic or aliphatic hydroxyl groups of MeKL due
to accessibility by length of Cl-PLA chain even if the acylation of both phenolic and
aliphatic hydroxyl groups in lignin could be widely achieved in the presence of
pyridine solvent system (Kim et al. 2015). Thus, it is concluded that copolymer-
ization of PLA onto MeKL occurred randomly at the sites of either phenolic or
aliphatic hydroxyl groups.

Table 1 Elemental composition of KL and MeKL

Elemental composition (wt%)

C H N Oa S

Kraft lignin 61.2 5.5 0.6 28.6 4.1

Methanol-soluble kraft lignin 61.3 5.5 0.3 30.4 2.5
a
Oxygen content = 100 - (carbon ? hydrogen ? nitrogen ? sulfur)

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Table 2 Molecular weights (g/mol) and polydispersity index (PDI) of the synthetic PLA and MeKL-g-
PLA copolymers
Samples Man (g/mol) PDIa Yield (%)

Synthetic PLA1 5400 1.30 67.1 ± 1.1

Synthetic PLA2 12,000 1.17 69.2 ± 1.4
Synthetic PLA3 25,000 3.12 76.0 ± 1.3
MeKL-g-PLA1 9,000,000 1.70 31.2 ± 0.9
MeKL-g-PLA2 5,400,000 1.64 26.8 ± 1.3
MeKL-g-PLA3 1,100,000 2.18 25.6 ± 1.2

MeKL: Mn = 16,000 g/mol; PDI = 6.19

a
Determined by GPC-MALLS analysis

Fig. 2 FT-IR spectra of synthetic PLA2, MeKL, and the MeKL-g-PLA copolymers

The resulting MeKL-g-PLA copolymers were found to be soluble in organic

solvents such as DMSO and DMF; however, they were not soluble in PLA-
dissolving solvents such as chloroform and dichloromethane. By the way, the
content of each MeKL and PLA in MeKL-g-PLA copolymer could not be
determined because the unreacted MeKL and Cl-PLA were thoroughly removed by
washing with excess amount of methanol and subsequent DCM after the
copolymerization.
The chemical structure of the MeKL-g-PLA copolymers was examined by FT-IR
as well as NMR analysis. The FT-IR spectra confirmed the incorporation of PLA, as
evidenced by the presence of the C=O stretching vibration at 1754 cm-1 as well as
the –CH3 and –CH symmetric and asymmetric vibrations at 2997 and 2947 cm-1,
respectively (Fig. 2). In addition, in the case of MeKL, a broad signal related to O–

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H stretching was observed at 3100–3500 cm-1, while weak signals related to the
stretching of the C=C aromatic ring were seen at 1605 and 1515 cm-1. However,
the copolymerization of MeKL with PLA led to a decrease in the intensity of the
C=C aromatic ring stretching bands as well as those of the signals related to the
indistinct O–H stretching band, indicating that the copolymerization occurred at the
OH positions.
Figure 3 shows the 1H NMR spectra of pure synthetic PLA1 (Mn of 5400 g/mol),
the copolymer MeKL-g-PLA1, and MeKL. It can be seen that the signals associated
with the methoxyl groups (3.5–4.0 ppm) and the aromatic ring (6.3–7.9 ppm) of
MeKL (Fig. 3c) were also observed in the case of MeKL-g-PLA1 (Fig. 3b). The
signals of methyl and methine protons associated with the PLA in the MeKL-g-
PLA1 are also observed at 1.46 and 5.20 ppm, respectively (Fig. 3b). Taking into
consideration both the chemical structure (FT-IR and NMR spectra) and molecular

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weight analysis (GPC-MALLS), it is concluded that copolymerization of MeKL

with PLA successfully occurred.

Thermal properties of MeKL-g-PLA copolymers

The TGA and DSC thermograms of MeKL, the MeKL-g-PLA copolymers

corresponding to PLA Mn values of 5400–25,000 g/mol, and synthetic PLA2 (Mn
12,000 g/mol) are shown in Figs. 4 and 5, respectively. The TGA thermograms
showed similar behaviors in the initial stage of the thermal degradation process. The
synthetic PLA2 started undergoing degradation at a temperature higher than 300 °C
and decomposed completely at 483 °C. In contrast, MeKL appeared to decompose
gradually, exhibiting a weight loss of approximately 58 % at 600 °C. The TGA
thermograms of the copolymers MeKL-g-PLA1 and MeKL-g-PLA2 showed
behaviors similar to that of the thermogram for MeKL. The copolymer MeKL-g-
PLA3 underwent rapid degradation like PLA. This was likely because of the length
of the PLA chains copolymerized onto MeKL.
The synthetic PLA2 sample showed a glass-transition temperature (Tg) of
approximately 49 °C and a melting temperature (Tm) of approximately 157 °C;
however, it did not show a crystallization temperature (Tc). In the literature, various
ranges from 40–75 and 130–230 °C were reported for Tg and Tm of PLA,
respectively (Henton et al. 2005; Moon et al. 2001). Therefore, Tg and Tm of
synthetic PLA2 were lower than those of commercial PLA due to its low molecular
weight.
In general, the commercial lignin and organosolv lignin exhibit Tg values of 158
and 144 °C, respectively, according to Gordobil et al. (2014). However, Tg value of
58 °C was observed in the MeKL, but the Tg, Tc, and Tm values of the MeKL-g-PLA
copolymers were 51.1–51.9, 85.4–91.7, and 141.5–149.4 °C, respectively. Conse-
quentially, the incorporation of PLA into MeKL slightly increased the Tg and
decreased the Tm, compared to the synthetic PLA2 (Fig. 5).

Fig. 4 TGA thermograms of MeKL, synthetic PLA2, and the MeKL-g-PLA copolymers

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Fig. 5 DSC thermograms of MeKL, synthetic PLA2, and the MeKL-g-PLA copolymers after the third
heating scan

Table 3 Tensile strengths and Young’s modulus of the MeKL-g-PLA and synthetic PLA specimens
Specimens Tensile strength (MPa) Young’s modulus (GPa)

MeKL-g-PLA1 3.57 ± 0.68 0.38 ± 0.08

MeKL-g-PLA2 3.77 ± 1.57 0.44 ± 0.09
MeKL-g-PLA3 3.80 ± 0.36 0.45 ± 0.01
Synthetic PLA3 0.83 ± 0.06 0.04 ± 0.01

Tensile strengths of MeKL-g-PLA specimens

The tensile strength of the MeKL-g-PLA copolymers was measured in order to

determine the effects of varying the molecular weight of PLA1–3. The test
specimens were made by injection molding as described in experimental
section. Table 3 shows the results of the tensile test performed on the MeKL-g-
PLA specimens and pure synthetic PLA3 (25,000 g/mol). In general, tensile
properties for commercial PLA (75,000–169,000 g/mol) were shown to have a
tensile strength of 57–65 MPa and Young’s modulus of 1.02–3.25 GPa (Gordobil
et al. 2014; Bledzki et al. 2009; Murariu et al. 2008; Garlotta 2001; Jacobsen and
Fritz 1999). However, the tensile strength and Young’s modulus of synthetic PLA3
showed to be 0.83 and 0.04 GPa, respectively, which was lower, compared with
commercial PLA. Those poor mechanical properties may be because of PLA3 low
molecular weight and PDI. Furthermore, the MeKL (16,000 g/mol) and synthetic
PLA1–2 of 5400–12,000 g/mol could not accomplish mechanical test because they
were broken too easily on the mold.
Consequently, copolymerization of MeKL and PLA1–3 led to an increase of the
tensile strength 3.5–3.8 MPa, 4.5-fold increase, compared with synthetic PLA3.
Further, the tensile Young’s moduli of MeKL-g-PLA1-3 copolymers did not differ

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significantly and increased only slightly with an increase in the PLA Mn value.
However, their mechanical properties were lower than those of lignin/PE (about
13–5 MPa), lignin/PP (about 35–20 MPa), cellulolytic enzyme lignin/PLA (about
60–40 MPa), and lignin/PLA (homogeneous poly-L-lactic acid) blends (47–23 MPa)
in previous other studies (Ouyang et al. 2012; Li et al. 2003; Alexy et al. 2000).

Conclusion

In this work, MeKL-g-copolymers were successfully synthesized from MeKL by

graft polymerization of PLA with Mn values of 5400–24,000 g/mol. The resulting
Mn of MeKL-g-PLA copolymers was significantly increased up to
*9,000,000 g/mol. Notably, the overall Mn (MeKL-g-PLA copolymer1) was more
increased among MeKL-g-PLA copolymers when the smaller size of PLA1 was
used for copolymerization, implying that the small length of PLA chain could easily
access onto MeKL during the copolymerization. The thermal properties of the
MeKL-g-PLA copolymers were not significantly improved compared to those of
synthetic PLA. However, their glass-transition temperature was slightly higher, and
their melting temperature was slightly lower than that of synthetic PLA. In addition,
those lignin-g-copolymers have shown an increase in the tensile strength and
Young’s modulus, by 4.5-fold and tenfold, respectively, compared with synthetic
PLA. Taken together, these chemical and physical characteristics suggest that the
copolymerization of lignin can be considered as a useful method for the utilization
of a technical lignin as lignin-based biomaterials.

Acknowledgments This study was supported by the Research Fellowship of the National Institute of
Forest Science in 2015 and the financial supports of National Institute of Forest Science (FP0400-2015-
01).

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