Research Article

pubs.acs.org/journal/ascecg

Renewable High-Performance Polyurethane Bioplastics Derived from

Lignin−Poly(ε-caprolactone)
Yan Zhang,*,† Jianjun Liao,† Xiangchen Fang,*,‡ Fudong Bai,‡ Kai Qiao,‡ and Lingmin Wang‡
†
Shanghai Key Laboratory of Advanced Polymeric Materials, Key Laboratory for Ultrafine Materials of Ministry of Education, School
of Materials Science and Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R.
China
‡
Fushun Research Institute of Petroleum and Petrochemicals, SINOPEC, 31 Dandong Road, Fushun 113001, Liaoning, P. R. China
*
S Supporting Information
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ABSTRACT: Here, we report novel lignin-poly(ε-caprolac-

tone)-based polyurethane bioplastics with high performance.
The poly(ε-caprolactone) (PCL) was incorporated as a
biodegradable soft segment to the lignin by the bridge of
hexamethylene diisocyanate (HDI) with long flexible aliphatic
chains and high reactivity. The effects of -NCO/-OH molar
ratio, content of lignin, and molecular weight of the PCL on
the properties of the resultant polyurethane plastics were
thoroughly evaluated. It is important that the polyurethane
film still possessed high performance in the tensile strength,
breaking elongation, and tear strength, which could reach
19.35 MPa, 188.36%, and 38.94 kN/m, respectively, when the
content of lignin reached as high as 37.3%; moreover, it was
very stable at 340.8 °C and presented excellent solvent-resistance. The results demonstrated that the modification of the lignin
based on the urethane chemistry represents an effective strategy for developing lignin-based high-performance sustainable
materials.
KEYWORDS: Lignin, Polyurethane, Poly(ε-caprolactone), Bioplastics, High performance

■ INTRODUCTION
Lignin, as the second most abundant natural polymer and cost-
effective byproduct from the papermaking and biorefinery
industries, has been considered as a valuable substitute for some
petrochemical products. Currently, they are generally con-
sumed as biorenewable fuel,1 as chemical reagents,2 as
fertilizer,3 as fillers,4 as adhesives,5,6 and in other low-value
applications.7−10 Thus, it is urgent to develop new strategies for
the valorization of lignin as an abundant component for the
production of high-value-added and sustainable materials.
Lignin-containing recyclable plastics have recently arisen as
an active field. For example, Naskar’s group reported a novel
lignin-derived thermoplastic with telechelic polybutadiene as
soft segments.11 Afterward, this group reported an improved
strategy to synthesize polyurethane (PU) thermoplastics from
lignin by changing the functional groups from carboxylic acids
to isocyanates in the rubbery segment. The mechanical
properties of the resultant copolymers were improved in
comparison with the lignin due to the occurrence of the
urethane covalent bonds.12 Also, lignin-based thermoset plastics
have been reported by the Turri group.5 They presented novel
thermoset PU coatings by cross-linking the commercial
softwood kraft lignin with toluene diisocyanate (TDI) at
different NCO/OH ratios. In addition, Sun’s group synthesized
a novel biofoam by replacing commercial polyol with different
amounts of lignin (8.33−37.19% w/w) in traditional PU
production, and its thermal stabilities were slightly improved.13
However, to the best of our knowledge, there are few reports
on the lignin-based polymers uniting the high-performance and
high-content lignin.
Poly(ε-caprolactone) (PCL) is one of the main biodegrad-
able polymers in the current and emerging bioplastics markets.
The incorporation of PCL to the lignin has been studied by
several groups by “graft to” or “graft from” methods. The boron
end-functionalized PCL was grafted to the lignin by the
formation of arylboronate ester linkages.14 In addition, the
lignin-based polyurethane was prepared based on the lignin,
PCL, and 4,4′-methylene-diphenylene diisocyanate (MDI).15
These pieces of research placed emphasis on the synthesis
method while the mechanical properties have not been well
studied. Furthermore, the lignin−PCL copolymer was synthe-
sized by ring-opening polymerization (ROP) of ε-caprolactone
(CL) initiated by the hydroxyl groups on the lignin.16 However,
it is hard to strike a balance between the high content of lignin
(>30 wt %) and maintaining the performance of the lignin−
PCL copolymer.
Received: January 27, 2017
Revised: March 10, 2017
Published: April 2, 2017

© 2017 American Chemical Society 4276 DOI: 10.1021/acssuschemeng.7b00288

ACS Sustainable Chem. Eng. 2017, 5, 4276−4284
ACS Sustainable Chemistry & Engineering Research Article

It is well-known that lignin contains various functional Table 1. Synthesis of the Different LPUs with the
groups including aliphatic and phenolic hydroxyl, methoxyl, Corresponding Designations and Formulations
carbonyl, and carboxyl moieties;17 these reactive groups have
-NCO/- Wlignin/WPCL Molecular weight of
effectively enabled the preparation of the lignin-containing Samples OH (g/g) Clignin(%)a PCL
products, such as epoxies,18 phenolics,19 polyurethanes,20 etc.
LPU-1 0.5 5/10 29.24 500
Herein, a novel renewable polyurethane film with a high
LPU-2 1.0 5/10 26.03 500
content of lignin was successfully achieved based on the
LPU-3 1.2 5/10 24.94 500
urethane chemistry; the hexamethylene diisocyanate (HDI)
LPU-4 1.35 5/10 24.18 500
with long flexible aliphatic chains was used as activator for the
LPU-5 1.5 5/10 23.47 500
hydroxyl groups of the lignin, and the PCL was incorporated as LPU-6 1.75 5/10 22.36 500
a biodegradable soft segment to improve the flexibility of the LPU-7 2.0 5/10 21.36 500
lignin-based polyurethane. The resultant lignin-derived polyur- LPU-8 1.35 5/10 27.16 1000
ethane films exhibited excellent mechanical properties; more- LPU-9 1.35 5/10 28.95 2000
over, the available biobased soft segment PCL and lignin could LPU-10 1.35 5/0 81.49 500
make the polyurethane film a completely renewable plastic.

■
EXPERIMENTAL SECTION
Materials. Alkali lignin was purchased from Wuhan East China
Chemical Co., Ltd. (Wuhan, China). Poly(ε-caprolactone) glycol
(PCL, CAPA 2054, Mn = 500; CAPA 2100, Mn = 1000; CAPA 2201,
Mn = 2000) was supplied by Perstorp (Sweden). Stannous octoate
(Sn(Oct)2) and HDI were provided by Sigma-Aldrich. NaOH, HCl,
and N,N-dimethylformamide (DMF) were purchased from Sinopharm
Chemical Reagent Co., Ltd. DMF was distilled over calcium hydride
before use.
Purification of the Lignin. The lignin was purified before use.
Briefly, raw alkali lignin (50.0 g) was dispersed in water (500 mL) and
then stirred. The pH value of the suspension was adjusted to 12 with 1
M NaOH aqueous solution. The heterogeneous mixture was
centrifuged at the speed of 6000 rpm for 15 min, and the supernatant
was decanted followed by filtration. One mole of aqueous HCl was
slowly added to the supernatant until the pH value reached 3, and the
mixture was centrifuged at the speed of 6000 rpm for 15 min. After
that, the supernatant was decanted, the precipitation was resuspended
in 500 mL of distilled water, and the procedure was repeated until the
pH value of the filtrate reached neutral. The precipitated lignin was
dried under vacuum at 70 °C for 24 h, and the yield of the purified
lignin was about 20%. The content of the hydroxyl groups was
determined using the method described by Kang.21 The batch of alkali
lignin used in these studies had a total hydroxyl content of 1.99 mmol/
g.
Synthesis of the Lignin−PCL Polyurethane (LPU). The
hydroxyl groups of the lignin were activated by HDI, and then the
PCL was incorporated by the reaction between the NCO groups of
HDI and the OH groups of PCL. A series of lignin−PCL
polyurethanes (LPUs) were prepared by adjusting -NCO/-OH (the
molar ratio of isocyanate groups of HDI to hydroxyl groups of the
lignin and PCL), the content of lignin, and the molecular weight of
PCL. The -NCO/-OH ratio was calculated using eq 1:
WHDI × [NCO]HDI
‐NCO/‐OH =
Wlignin × [OH]lignin + WPCL × [OH]PCL (1)
where WHDI, Wlignin, and WPCL represent the weights of HDI, lignin,
and PCL, respectively; [NCO]HDI is the molar content of isocyanate
groups in HDI; [OH]lignin and [OH]PCL are the molar contents of total
hydroxyl groups in the lignin and PCL, respectively.
The experimental conditions for preparing the LPU are given in
Table 1.
Typically, the purified alkali lignin (5.00 g) was dissolved in
anhydrous DMF (50 mL) in the reaction flask at 70 °C for 3 h under
magnetic stirring. A total of 45 μL of Sn(Oct)2 (0.025 g, 0.62 mmol, 5
wt‰ based on the mass of lignin) in dry toluene stock solution was
added into the flask as a catalyst under the protection of argon by
using a microliter syringe, and the exhausting−refilling process was
repeated several times to remove toluene. Afterward, the HDI (5.00
mL, -NCO/-OH = 1.35) was added to the mixture and allowed to
LPU-11 1.35 5/3.75 43.15 500
LPU-12 1.35 5/5 37.30 500
LPU-13 1.35 5/6.25 32.84 500
LPU-14 1.35 5/7.5 29.34 500
a Wlignin
C lignin = × 100%.
Wlignin + WPCL + WHDI
react for 3 h at 70 °C; then the PCL (10.00 g) was added to the
reactor for another 10 h at 70 °C.
Preparation of the LPU Film. The LPU film was fabricated by the
spin-cast method. After the polymerization, the mixture prepared in
the previous section was immediately spin-cast onto the PTFE board
in air and allowed to cross-link in a ventilated oven at 70 °C for 24 h;
then the LPU film was obtained.
Characterization. Fourier-Transform Infrared Spectroscopy
(FTIR). The infrared spectra of the purified lignin and LPU were
determined using a Nicolet 5700 FTIR spectrometer. The LPU
samples were measured by the KBr tablet method and scanned from
4000 to 400 cm−1 with a resolution of 4 cm−1.
X-ray Diffraction (XRD). X-ray diffraction patterns were recorded by
monitoring the diffraction angle 2θ from 10° to 60° on a Philips X’Pert
PRO instrument under a voltage of 40 kV and a current of 40 mA.
Water Contact Angle (WCA). The WCA measurements on the PU
films were performed using a contact angle meter (POWEREACH,
JC2000D2) at room temperature, and deionized water was used as
probe liquid.
Scanning Electron Microscopy (SEM). The surface features of the
film were observed by SEM (Hitachi S-3400N, Hitachi High
Technologies, Inc., Tokyo, Japan). The films placed on conductive
tapes were sputter coated with gold and observed at an acceleration
voltage of 15 kV.
Thermogravimetric Analysis (TGA). Thermal gravimetric analysis
(TGA) was performed with a STA449 F3 from Netzsch at a heating
rate of 10 °C/min from 40 to 600 °C under nitrogen atmosphere. The
weight of the samples was 5−7 mg; the rate of gas consumption was
40 mL/min.
Tensile Test. The tensile tests of LPU films for the tensile strength
and elongation at break were performed according to GB/T 1040
standard on a CMT 2206 (SANS) tensile tester. The right-angle tear
strength was performed following the QB/T 1130 method on a CMT
2206 (SANS) tensile tester. All samples for tensile testing were
conditioned at 25 °C and 50% humidity for 24 h prior to the test, and
the tensile tests were carried out under similar conditions. Five
specimens of each type were tested, and the average values were
reported.
Swelling Test. The swelling rate was conducted in DMF at a
constant temperature of 25 °C for 72 h to reach equilibrium. After
swelling, the excess solvent on the surface of each sample was removed
by filter paper and the swollen films were weighed. The swelling rate
was determined by the corresponding eq 2:
m − m0
Swelling Rate = s × 100%
m0 (2)

4277 DOI: 10.1021/acssuschemeng.7b00288

ACS Sustainable Chem. Eng. 2017, 5, 4276−4284
ACS Sustainable Chemistry & Engineering
Scheme 1. Synthesis Route of the LPU
where m0 is the mass of the dry LPU film before swelling (g) and ms is
the mass of the LPU film after swelling (g).
The cross-linking density of the LPU flims (νc/V0, unit: mol cm−3)
was calculated by the Flory−Rethner equation:
v + χv 2 + ln(1 − v)
vc /V0 = − 2
V1 × (2v1/3 − v) (3)
where νc is the effective number of cross-links (mol), V0 is the volume
of dry polymer (cm3), V1 is molar volume of DMF (76.87 mL mol−1),
χ is the polyurethane−DMF interaction parameter (0.40),22 ν is the
volume fraction of polyurethane in the swollen gel (ν = V0/V), and V
is the volume of the swollen gel at equilibrium (cm3).
■ RESULTS AND DISCUSSION
Synthesis of the LPU. The synthesis route of the LPU was
depicted in Scheme 1. The LPU was prepared following two
steps. First, the isocyanate groups of HDI were utilized to
activate the hydroxyl groups in the lignin with Sn(Oct)2 as a
catalyst. Second, PCL was introduced into the activated lignin
via urethane linkages by a polyaddition reaction.
The structure of the LPU was confirmed by FTIR spectral
analysis. For the FTIR curve of the purified lignin in Figure 1, a
typical and intense signal at 3500−3300 cm−1 was assigned to
Figure 1. FTIR spectra of the purified lignin and the LPU.
4278
Research Article
the aromatic and aliphatic -OH stretching vibrations. The
absorption peaks at 2932 and 2864 cm−1 were attributed to the
symmetric and asymmetric -C−H stretching vibrations of the
methyl and methylene groups, and the peak at 1697 cm−1
belonged to the -CO stretching of the carbonyl groups.23
More specifically, the sharp absorption peaks which located at
1607, 1512, and 1459 cm−1 corresponded to the existence of
the aromatic ring.24 The main characteristic peaks of the
guaiacyl and syringyl units of lignin appeared at 1275, 1038
cm−1 and 1219, 1120 cm−1, respectively.25
Compared with the spectrum of the purified lignin, the FTIR
spectrum of the LPU displayed a narrow peak approximately at
3399 cm−1 and showed a new peak at 1536 cm−1, which were
attributed to -NH stretching vibrations and bending vibrations.
Meanwhile, two characteristic absorption peaks were found at
1733 cm−1 (-CO) and 1637 cm−1 (-NHCOO-), indicating
the reaction between -OH groups and -NCO groups. The peak
at 1258 cm−1 was associated with the -C−N stretching.26 In
addition, the PCL segment in the LPU was identified by the
increase of methylene -C−H bands (peak at 2862 cm−1). All
the features clearly indicated that the LPU copolymer
composed of PCL and lignin was successfully prepared.
Crystallinity. The X-ray diffraction was performed for the
purified lignin, PCL, and the LPU in an attempt to study the
crystallinity. As shown in Figure 2, the purified lignin showed
Figure 2. XRD patterns of PCL, lignin, and the LPU with different
molecular weights of PCL.
DOI: 10.1021/acssuschemeng.7b00288
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diffused signals at 2θ values of 32 and 46° and the PCL showed alkyl−ether linkages, dehydration and decarboxylation reac-
stronger crystal peaks at 2θ values of 22 and 24°.27,28 Also, the tions, the elimination of carbon dioxide and water, etc.29 While
same peaks at 32 and 46° have been observed in the LPU and the second stage (>300 °C, Tmax is 353.7 °C) was related to the
their intensity is weaker than that of the purified lignin. These decomposition reaction and the condensation reaction of
peaks are related to the hard segment (lignin) crystallization of aromatic rings, and also related to the cleavage of carbon−
LPU. What’s more, the crystallization behavior of LPU might carbon linkages in the lignin structure.30
be attributed to the crystallinity of PCL and the crystallization For the LPUs, it also can be observed that the decomposition
was affected by the molecular weight of PCL. In comparison process of LPU occurred as two stages: the first stage (200−
with the LPU-4 (the molecular weight of grafted PCL is 500), 375 °C) was associated with the decomposition of the urethane
the LPU-9 (the molecular weight of grafted PCL is 2000) groups and the phenolic hydroxyl groups of lignin.31,32 The
which incorporated the longer PCL chain showed the PCL second stage (375−500 °C, Tmax is about 440 °C) was ascribed
crystal peaks at 2θ values of 21 and 24° instead of the broad to the decomposition of ester bonds from the PCL and the
diffraction peak at 21°. It was possible that the shorter PCL rupture of carbon−carbon linkages between lignin structural
chain in an LPU network with a high degree of cross-linking is units. As can be noticed, the decomposition temperature of the
unable to move easily and does not show a crystalline first stage (200−375 °C) was higher than that of the purified
structure.16 While the longer PCL chain could form a lignin; these results indicate that the incorporation of PCL into
semicrystalline structure, thus resulting in poor mechanical lignin bridged by HDI could improve the LPU thermal stability
properties. at low temperature (<350 °C). This was attributed to the cross-
Thermal Properties of the LPU. The thermal decom- link reactions between HDI, PCL, and lignin, which could
position of LPU is an important determinant for the protect the hydroxyl groups in the lignin segment from
technological prospects of their application. TGA measure- dehydration.33
ments were performed to evaluate the thermal stability of LPU. The thermal decomposition temperatures at various mass
Figure 3 showed TGA curves of the purified lignin and LPU. loss percentages and the final char residue were summarized in
It was found that the purified lignin decomposed in two stages, Table 2. From Table 2, it is evident that the content of lignin
plays an important role in the thermal stability of LPUs. It can
be seen that the decomposition temperature at 5% mass loss
(T5%) increases from 255.3 to 285.4 °C when the content of
lignin decreases from 37.30 to 24.18%. These results indicated
that the lower lignin content improved the LPU thermal
stability at low temperature (<350 °C), which is related to the
lower decomposition temperature of lignin. Similarly, the trend
of T10% and T20% is consistent with that of T5%. However, the
trend of T50% showed an opposite direction. This is mainly
because the LPU has a mass loss dominated by decomposition
of a large number of C−O bonds in PCL (>350 °C).
Furthermore, it was also found that the char residue of LPUs
increased with the increase of the content of lignin, and the
char residue of purified lignin was 54.8%. The high char residue
was associated with the high thermal resistance of lignin due to
the large number of ether linkages and the highly aromatic
backbone in its chemical structure.34,35 These results indicate
that the lignin segment is the main source of residual LPU.
Mechanical Properties of the LPU Films. In order to
Figure 3. TGA curves under a stream of nitrogen of lignin and LPU. determine the mechanical performance of the LPU, the LPU
films were fabricated by the spin-cast method. The mechanical
and the temperature at the maximum rate of mass loss (Tmax) properties of the LPU have been studied in detail to evaluate
was 263.1 and 353.7 °C (Table 2). The first stage (70−300 °C, the influence of the factors, such as -NCO/-OH molar ratio, the
Tmax is 263.1 °C) was ascribed to the breaking of α- and β-aryl− lignin content, and the molecular weight of PCL.
Effect of -NCO/-OH Molar Ratio on the Mechanical
Table 2. Dynamic Thermal Properties of the Purfied Lignin Properties of the LPU Film. The properties of the thermoset
and LPU polymers depend on their network architecture. For the LPU,
HDI has a saturated aliphatic straight chain and acts as a spacer
TG/°C DTG to bridge lignin and PCL to form a network structure.
Sample T5%a T10% T20% T50% Tmax/°C Residue/% Therefore, the -NCO/-OH is regarded as an effective way to
LPU-4 285.4 320.5 342.8 383.3 359.7, 442.2 19.8
regulate the properties of LPUs.
LPU-14 290.9 321.7 342.4 387.8 357.2, 441.2 23.0
The effect of -NCO/-OH on the mechanical properties of
LPU-13 271.7 312.0 338.9 403.2 354.9, 441.0 23.0 LPU films were summarized in Table 3. As the -NCO/-OH
LPU-12 255.3 301.9. 332.5 424.4 340.8, 429.8 25.2 increased from 0.5 to 1.75, the tensile strength increased from
lignin 169.3 233.5 307.9 263.1, 353.7 54.8 0.17 to 25.65 MPa, which was mainly attributed to the fact that
there were more isocyanate groups to cross-link with hydroxyl
a
T5% represents the degradation temperature at 5% mass. The number groups and the cross-link density increased with the increase of
5 represents mass loss; the others are the same. Tmax is the temperature -NCO/-OH. However, with the further increase of the -NCO/-
at the maximum rate of mass loss. OH from 1.75 to 2.0, the tensile strength slightly decreased
4279 DOI: 10.1021/acssuschemeng.7b00288
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ACS Sustainable Chemistry & Engineering Research Article

Table 3. Effect of the -NCO/-OH Ratio on the Mechanical at break, and the tear strength, could reach 15.0 ± 1.9 MPa, 329
Properties of the Lignin-Based Filma ± 21%, and 57.7 ± 6.2 KN/m, respectively.36 The proper
content of lignin could increase the cross-link density and
σ (MPa) δ (%) Pb (kN/m)
provide a higher modulus; in the meanwhile, lignin may cause
-NCO/- Tensile Elongation at Right-angle tear the agglomeration and offset the promotion effect of the tensile
Sample OH strength break strength
strength. The increase of lignin content is an unbeneficial factor
LPU-1 0.5 0.17 ± 0.05 62.13 ± 1.66 b
to the elongation at break due to the cross-link structure, but it
LPU-2 1.0 2.78 ± 0.06 72.18 ± 3.08 8.59 ± 0.55 is a favorable factor to tear strength due to the higher modulus
LPU-3 1.2 5.21 ± 0.02 150.06 ± 6.62 18.01 ± 0.93 provided by lignin.
LPU-4 1.35 13.02 ± 0.41 296.95 ± 7.77 25.66 ± 0.64 Effect of the Molecular Weight of PCL on the Mechanical
LPU-5 1.5 19.24 ± 2.10 362.85 ± 17.40 35.50 ± 3.03 Properties of the LPU Film. PCL was incorporated as a
LPU-6 1.75 25.65 ± 1.39 229.22 ± 0.81 38.33 ± 4.51 biodegradable soft segment to the lignin; therefore, the intrinsic
LPU-7 2.0 22.89 ± 2.63 223.26 ± 11.59 38.32 ± 5.04 properties of PCL have significantly affected the mechanical
properties of the LPU film.
a
Note: The reactions were carried out at the PCL molecular weight
500 and mlignin/mPCL = 5/10. bThe tear strength of the film was not Table 5 summarized the effect of the molecular weight of
measured due to the difficulty in sample preparation with the required PCL on the mechanical properties of LPU films. As shown in
dimensions.
Table 5. Effect of the Molecular Weight of PCL on the
from 25.65 to 22.89 MPa. The negative effect was caused by the
Mechanical Properties of the Lignin-Based Filma
higher degree of cross-linking, which would result in stronger
intermolecular forces and more difficult movement of the chain σ (MPa) δ (%) Pb (kN/m)
segments. Similar impact occurred on the elongation at break Molecular
and tear strength with the increase of the -NCO/-OH, which is weight of Tensile Elongation at Right-angle
consistent with tensile strength. Moreover, it was found that the Sample PCL strength break tear strength
high performance of the LPU films mainly occurred at high LPU-4 500 13.02 ± 0.41 296.95 ± 7.77 25.66 ± 0.64
-NCO/-OH. It was deduced that the reactivities of the aliphatic LPU-8 1000 4.60 ± 0.36 126.68 ± 6.57 18.87 ± 0.78
b
hydroxyl and phenol hydroxyl in lignin molecules are different; LPU-9 2000
thus, more HDI should be added to improve the reaction a
Note: The reactions were carried out at -NCO/-OH = 1.35 and
degree of the lignin. mlignin/mPCL = 5/10. bTensile strength, right-angle tear strength, and
Effect of the Content of Lignin on the Mechanical elongation-at-break were not measured due to the inferior mechanical
Properties of the LPU Film. Lignin plays two roles: as the high- property.
modulus provider and the cross-linking agent for LPU.
Therefore, the content of lignin is closely linked with the
performance of LPU. The effect of the content of lignin on the Table 5, the molecular weight of PCL had an adverse effect on
mechanical properties of LPU films were summarized in Table the elongation at break, the tensile strength, and the right-angle
4. The tensile strength has a nonlinear relationship with the tear strength. The tensile strength slightly decreased from 13.02
to 4.60 MPa with increasing the molecular weight of PCL from
Table 4. Effect of Lignin Content on the Mechanical 500 to 1000. When the molecular weight of PCL reached 2000,
Properties of the Lignin-Based Filma the film was too brittle to test. It was acceptable that the
variation of the performance could be attributed to the cross-
σ (MPa) δ (%) Pb (kN/m) link density and the crystallinity of the LPU. The increase of
Tensile Elongation at Right-angle tear the molecular weight of PCL would decrease the density of the
Sample Clignin(%) strength break strength hydroxyl groups and resulted in a decreased cross-linking
LPU-4 24.18 13.02 ± 0.41 296.95 ± 7.77 25.66 ± 0.64 density accordingly. Moreover, the grafted PCL segment forms
LPU-14 29.34 11.86 ± 0.15 259.86 ± 11.25 24.72 ± 0.75 a semicrystalline structure when the molecular weight of PCL is
LPU-13 32.84 16.23 ± 0.79 233.05 ± 11.25 35.50 ± 3.03 higher than 500, which is responsible for the loss of tensile
LPU-12 37.30 19.35 ± 0.96 188.36 ± 7.73 38.94 ± 1.17 strength.16 As a result, the previous flexible network was
LPU-11 43.15 15.45 ± 1.23 29.15 ± 13.56 45.09 ± 2.99 destroyed and the materials demonstrated a brittle nature.
LPU-10 81.49 b Morphology of the LPU Films. Figure 4 shows the SEM
a
Note: The reactions were carried out at the PCL molecular weight images of the LPU films with different formulations. It is seen
500 and -NCO/-OH = 1.35. bTensile strength, right-angle tear that the surfaces of the LPU films become smoother and the
strength, and elongation-at-break were not measured due to the elasticty of the films increases with the increase of -NCO/-OH.
inferior mechanical property. In Figure 4a, the small grains set on the surface could be the
conglomeration formed by the lignin failing to incorporate into
content of lignin. The tensile strength decreased when the the polymeric network structure. It is deduced that the hydroxyl
content of lignin increased from 29.34% to 37.30%, while it groups in the lignin could not be fully activated at low values of
increased when the content of lignin further increased from -NCO/-OH, and the lignin had low activity accordingly. The
37.30% to 43.15%. When the lignin overage is too much results confirmed that the excess HDI could form the uniform
(>43.15%), the agglomeration of lignin would cause the drop of film, and the higher values of -NCO/-OH are favorable for the
the mechanical properties and the LPU film was shown to be formation of a smoother surface. The influence of the content
brittle. Moreover, the LPU had a hard, brittle nature and was of lignin is contray to the -NCO/-OH. Figure 4d represents a
difficult to be tested when there was no PCL incorporation. rougher surface when the content of lignin is 43.15%, and the
While the mechanical properties of the PU derived from the surfaces of the LPU films became smoother with the decrease
PCL-diol and HDI, such as the tensile strength, the elongation of the content of lignin. As presented in Figure 4h, the LPU
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ACS Sustainable Chemistry & Engineering
Figure 4. SEM image of the surfaces of LPU films with different -NCO/-OH at 1.0 (a), 1.2 (b), and 2.0 (c); different contents of lignin at 43.15%
(d), 32.84% (e), and 29.34% (f); and different molecular weights of PCL at 500 (g) and 2000 (h).
film showed a phase separation structure, which was related
with the PCL segment crystallization. It is worth noting that the
reason for the surface roughness is different, the grain size on
the LPU surfaces decreased with the increase of -NCO/-OH,
but the granular zone reduced with the decrease of content of
lignin. Compared with the surface, the cross-sectional
morphologies (Figure S2) of the LPU films are not porous
but smooth. The reason for this difference could be attributed
to the surface tension change during the drying process of
preparation of the LPU film. Only when the lignin content of
LPU is higher than 40 wt % will the cross-sectional morphology
of the LPU film be rough, and that is caused by the imcomplete
reaction of the lignin.
Wettability. Water contact angle measurements were
performed to determine the wettability properties of surfaces
of the LPU films. As indicated in Table S1, the wettability of
the LPU films was determined to some extent by the hydroxyl
groups on the surface. The lignin molecules contain a large
number of carboxyl and hydroxyl groups and show more
hydrophilic behavior than the PCL. Thus, the water contact
angles decreased with the increase of the content of lignin. The
value of -NCO/-OH also affects the water contact angles. As
shown in Figure 5, the LPU films exhibited adjustable
wettability and the water contact angles of the LPU films
increased from 64.4° to 94.6° due to the consumption of
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Figure 5. Water contact angle of LPU films with different -NCO/-OH
at 1.0 (a), 1.35 (b), and 2.0 (c).
hydroxyl groups caused by the increase of -NCO/-OH. The
wettability property can be adjusted according to practical
application to increase the value in use.
Swelling Properties of the LPU Films. The effects of the
-NCO/-OH, the content of lignin, and the molecular weight of
PCL on the cross-link densities and swelling rate in DMF are
shown in Figure 6. Figure 6a showed the effect of -NCO/-OH
on the cross-link density and the degree of swelling. It is clear
that the cross-linking densities increase from 3.14 to 45.10 ×
10−3 mol/cm3 with the -NCO/-OH increase from 1.0 to 2.0.
The swelling rate shows the opposite trend with the cross-
linking density as expected. This phenomenon could be
explained by the fact that there were more isocyanate groups
to cross-link with the hydroxyl groups of PCL, and a more
dense network structure formed, which would lead to a
DOI: 10.1021/acssuschemeng.7b00288
ACS Sustainable Chem. Eng. 2017, 5, 4276−4284
ACS Sustainable Chemistry & Engineering
Figure 6. Effect of -NCO/-OH (a), the content of lignin (b), and the molecular weight of PCL (c) on the swelling rate and cross-linking density of
the LPU.
Scheme 2. Schematic Representation of the LPU Networks
decreased ability of polymer chains to accommodate a solvent
molecule as the -NCO/-OH increases.
Figure 6b illustrated the degree of swelling and the cross-
linking densities as a function of the content of lignin in LPUs.
The swelling rate decreased from 246.44 to 193.38% with the
content of lignin increasing from 24.18 to 43.15%. However,
the cross-linking densities increased from 4.25 to 5.08 × 10−3
mol/cm3 when the content of lignin increased from 24.18 to
43.15%. Lignin as a cross-linking agent would form much more
cross-linking points and result in an increase of the cross-
linking density; thus, the swelling rate decreased accordingly.
Figure 6c displayed the effect of the molecular weight of PCL
on the degree of swelling and the cross-linking densities. The
swelling rate increased from 246.44 to 256.98% with the
increase of the molecular weight of PCL. It is deduced that the
increase of the molecular weight of PCL would decrease the
density of the hydroxyl groups and increase the distance
between the cross-linking points.
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The schematic presentation of the formation mechanism of
the LPU nerwork structure was dipicted in Scheme 2. The
network of the LPU was determined by the cross-link density
and the crystallinity. The hydroxyl groups in lignin were
activated by HDI, and the reactivity enhanced accordingly with
the increase of -NCO/-OH, which resulted in an increased
higher cross-link density, and thus, stronger intermolecular
forces occurred. The moderate cross-linking increased the
tensile strength and solvent-resistance of the films. However,
the movements of the chain segments are confined, with an
overincrease of -NCO/-OH, and this caused the negative effect
on mechanical properties. The lignin is not only the high-
modulus provider, but also the cross-linking agent. With the
increase of the content of lignin, the role as a cross-linking
agent became more important and led to the rise of the cross-
link density. Meanwhile, lignin can produce the stress
concentration points, but the tensile strength would not drop
rapidly because the lignin can provide the higher modulus as
well. However, the overage of lignin may cause the
DOI: 10.1021/acssuschemeng.7b00288
ACS Sustainable Chem. Eng. 2017, 5, 4276−4284
ACS Sustainable Chemistry & Engineering
agglomeration, which led to a worse membrane performance.
PCL was incorporated as a biodegradable soft segment to the
lignin, and the increase of the molecular weight of PCL would
decrease the density of the hydroxyl groups and resulted in a
decreased cross-link density. Meanwhile, the grafted PCL
chains formed a semicrystalline structure, and the PCL/lignin
phase segregation occurred, which is responsible for the loss of
the mechanical properties
■
CONCLUSION
The high-performance LPU film with high lignin content was
successfully achieved by the incorporation of PCL as a
biodegradable soft segment to the lignin by the bridge of
HDI with long flexible aliphatic chains and high reactivity. All
films were characterized in terms of physical, thermal, and
mechanical properties. The LPU film has better thermal
stability compared with the purified lignin. Moreover, the
adjustment of the content of lignin, -NCO/-OH, and the
molecular weight of PCL were effective ways to control the
mechanical properties of LPU films, and the properties of LPU
were dependent on their network architecture. The LPU had
excellent mechanical properties and could meet the daily use
even when the lignin content reached as high as 37.3%. The
incorporation of a soft segment of PCL into lignin could
improve the strength of the lignin and expand the applications
of lignin. The successful fabrication of the lignin-based
polyurethane bioplastics represents an effective strategy to
enhance the processability of lignin and develop sustainable
materials in the bioplastic field, such as sealing materials,
biodegradable packaging films, and bioadhesives.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acssusche-
meng.7b00288.
1
H NMR spectra of acetylated lignin and lignin; cross-
sectional morphologies of LPU films; and water contact
angles of the LPU films at varying formulations (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: zhang_yan@ecust.edu.cn; Tel: +86-21-65243432.
*E-mail: fangxiangchen.fshy@sinopec.com; Tel: +86-24-
56389569.
ORCID
Yan Zhang: 0000-0002-5022-362X
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
Financial support from the National Natural Science
Foundation of China (21274039), Shanghai Pujiang Program
(14PJD014), 111 Project (B14018), Specialized Research Fund
for the Doctoral Program of Higher Education
(20130074110007), and National Key Research and Develop-
ment Program (2016YFC1100700) is gratefully acknowledged.
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Research Article
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4284 DOI: 10.1021/acssuschemeng.7b00288

ACS Sustainable Chem. Eng. 2017, 5, 4276−4284