International Journal of Biological Macromolecules 193 (2021) 1400–1408

Contents lists available at ScienceDirect

International Journal of Biological Macromolecules

journal homepage: www.elsevier.com/locate/ijbiomac

Preparation and properties of novel bio-based epoxy resin thermosets from

lignin oligomers and cardanol
Guifeng Liu, Can Jin, Shuping Huo, Zhenwu Kong *, Fuxiang Chu *
Institute of Chemical Industry of Forest Products, CAF, Nanjing 210042, China
National Engineering Lab. for Biomass Chemical Utilization, Nanjing 210042, China
Key Lab. of Chemical Engineering of forest Products, National Forestry and Grassland Administration, Nanjing 210042, China
Key Lab. of Biomass Energy and Material of Jiangsu Province, Nanjing 210042, China
Co-Innovation Center of Efficient Processing and Utilization of Forest Resources of Jiangsu Province, Nanjing 210037, China

A R T I C L E I N F O A B S T R A C T

Keywords: A series of lignin-based epoxy resins (LEPs) were prepared by the reaction of epichlorohydrin with lignin olig­
Alkali lignin omers derived from partial reductive depolymerization of lignin. To overcome the high viscosity and brittleness
Cardanol defects in practical applications, the LEPs were blended with renewable epoxied cardanol glycidyl ether (ECGE)
Reductive depolymerization
and then cured with methyltetrahydrophthalic anhydride (MeTHPA) to form high-performance epoxy thermo­
Epoxy resin
sets. The effects of degree of lignin depolymerization, chemical composition of lignin oligomers and dosage of
Property
ECGE on thermal and mechanical properties of the cured products were investigated. The LEP/MeTHPA ther­
mosets exhibited good thermal and mechanical properties. Especially, by separating monomer-rich fractions
from lignin oligomers, the thermal and mechanical properties of the cured product were improved obviously.
Notably, the incorporation of ECGE also possessed a positive effect on reinforcing and toughening the cured
products. With 20 wt% ECGE loadings, the tensile, flexural and impact strength of the cured product reached the
maximum value of 77 MPa, 115 MPa and 14 kJ/m2, respectively, which were equivalent to the commercial
bisphenol A epoxy resins thermosets. These findings indicated that the novel bio-based epoxy resins from lignin
oligomers and cardanol could be utilized as renewable alternatives for BPA epoxy resins.

1. Introduction resins [10–21]. Among them, lignin, the largest renewable source of
aromatics on the earth, has been recognized as one of the most prom­
As one of the most important classes of polymeric materials, epoxy ising candidates for BPA to form epoxy resins [22–26]. Chemically,
resins are widely used in many application fields, such as coatings, ad­ lignin has a variety of functional groups, such as phenolic hydroxyl,
hesives, electronic encapsulating materials, packaging materials, high- alcohol hydroxyl and carboxylic acids, which provide active sites to be
performance composites and so on [1,2]. Particularly, approximately functionalized with epoxy groups. Moreover, the rigid aromatic skele­
90% of the commercial epoxy resins are synthesized from the reaction of tons of lignin could endow epoxy thermosets with excellent thermal and
bisphenol A (BPA) with epichlorohydrin. One of the most disadvantages mechanical properties [27–29]. Although lignin has great potentials for
in this synthetic rout is the use of BPA, which has been generally many industrial applications including the use in polymer systems,
considered to be harmful for human health and has negative effects on mesoporous carbon nanomaterials, hydrogels, carbon fibers and fuels
environment [3,4]. From the viewpoint of environmental preservation [30–33], the efficient utilization of lignin has been restricted seriously
and health concerns, extensive efforts have been conducted to search for due to its complex chemical structure and composition, low reactivity
an alternative method producing epoxy resins from sustainable and and poor solvent solubility [34]. Most of the lignin are usually treated as
nontoxic starting materials [5–9]. waste or burned as cheap fuel, which not only results in a great waste of
In recent years, various bio-based resources such as plant oil, resources but also brings serious environmental pollutions [35–37].
resveratrol, cardanol, tannins, lignin, eugenol, guaiacol, vanillin and Therefore, numerous efforts have been directed toward searching for an
sugar-based furan chemicals have been explored to produce green epoxy effective strategy to enhance the reactivity and solvent solubility of

* Corresponding authors.
E-mail addresses: [email protected] (Z. Kong), [email protected] (F. Chu).

https://doi.org/10.1016/j.ijbiomac.2021.10.203
Received 30 September 2021; Received in revised form 26 October 2021; Accepted 26 October 2021
Available online 3 November 2021
0141-8130/© 2021 Published by Elsevier B.V.
G. Liu et al. International Journal of Biological Macromolecules 193 (2021) 1400–1408

lignin [38–42]. Among these methods, the partial depolymerization of 2.3. Partial reductive depolymerization of lignin
lignin to obtain products with low molecular weight and more reactive
functional groups is thought to be one of the most prevalent and effec­ Alkali lignin (160 g), Pd/C (3.2 g) and ethanol (270 mL) were added
tive strategies, as well as the products derived from lignin depolymer­ into a 1 L autoclave equipped with a magnetic stirrer. The atmosphere
ization have been successfully applied for the preparation of bio-based was replaced with H2 completely, and the initial pressure was main­
epoxy resins [43–48]. Nevertheless, due to their inherent rigid struc­ tained at 4.5 MPa. The mixture was then heated to 275 ◦ C under
tures, these lignin-based epoxy resins always suffer from high viscosity, continuous stirring at 800 rpm, and the reaction was allowed to proceed
poor processability and the brittleness of the cured materials, which for 4 h, 8 h and 12 h to give depolymerized lignins (DLs: DL1, DL2 and
limited their applications. Furthermore, in order to design and tune the DL3) with different content of hydroxyl groups, respectively. After the
properties of epoxy thermosets, the influence of the degree of lignin reaction, the reactor was cooled to room temperature. The mixture was
depolymerization and the chemical composition of depolymerized filtered to recover the catalyst. The DLs were obtained after the ethanol
lignin on the physical and chemical properties of cured products also was removed from the collected filtrate by a rotary evaporator under
need a systematic investigation. reduced pressure at 40 ◦ C. The content of hydroxyl groups in alkali
In this work, for the purpose of developing novel bio-based epoxy lignin and DLs were summarized in Table 1.
resins with high performance, a series of lignin-based epoxy resins
(LEPs) were prepared through a highly efficient two-step process in 2.4. General procedure of the synthesis of lignin-based epoxy resins
which oligomers derived from reductive depolymerization of lignin
were used as raw materials. The LEPs were then cured with methylte­ The depolymerized lignin (100 g) was dissolved in epichlorohydrin
trahydrophthalic anhydride (MeTHPA) in a solvent-free process to form (1000 mL), trimethylbenzenemethanaminium chloride (TEBAC, 2 g)
epoxy thermosets, respectively. Furthermore, to overcome the intrinsic was added into the solution. The mixture was stirred at 110 ◦ C for 5 h.
high viscosity and brittleness of the LEPs for practical applications, the The resulted mixture was then cooled to 50 ◦ C, followed by the addition
epoxied cardanol glycidyl ether (ECGE), which is known as a reactive of NaOH (1.6 eq. the number of active OH groups in DL, determined by
dilutant and flexibilizer [12], was introduced into the curing systems to quantitative 31P NMR spectroscopy). The reaction mixture was stirred at
improve their processability and the toughness of the epoxy thermosets. 60 ◦ C for 5 h. After the completion of reaction, the TEBAC, NaCl and the
The chemical structures of the LEPs were characterized by FT-IR, 1H excess of NaOH were completely removed by washing with water.
NMR and 13C NMR. The effects of the degree of lignin depolymerization, Finally, the excess epichlorohydrin was distilled off under reduced
the chemical composition of depolymerized lignin and the addition of pressure at 120 ◦ C to afford a dark brown viscous liquid.
ECGE on thermal and mechanical properties of the cured products were Synthesis of LEP(1): Following the general procedure using DL1
systematically investigated. The results showed that the addition of (100 g, active OH groups 0.47 mol), epichlorohydrin (1000 mL, 9 mol),
renewable ECGE is a novel and effective way to enhance the mechanical TEBAC (2 g, 0.009 mol), and NaOH (30 g, 0.75 mol) to give LEP(1).
properties of LEPs, as well as the epoxy thermosets derived from lignin Synthesis of LEP(2): Following the general procedure using DL2
oligomers and cardanol were comparable to commercial bisphenol A (100 g, active OH groups 0.52 mol), epichlorohydrin (1000 mL, 9 mol),
epoxy resins thermosets in terms of their mechanical properties, which TEBAC (2 g, 0.009 mol), and NaOH (33 g, 0.83 mol) to give LEP(2).
provides a new strategy to achieve the sustainable development of epoxy Synthesis of LEP(3): Following the general procedure using DL3
materials. (100 g, active OH groups 0.54 mol), epichlorohydrin (1000 mL, 9 mol),
TEBAC (2 g, 0.009 mol), and NaOH (35 g, 0.86 mol) to give LEP(3).
2. Experimental section Synthesis of LEP(4): Following the general procedure using DL4
(100 g, active OH groups 0.46 mol), epichlorohydrin (1000 mL, 9 mol),
2.1. Materials TEBAC (2 g, 0.009 mol), and NaOH (29 g, 0.74 mol) to give LEP(4).

The ECGE with epoxy equivalent weight (EEW) of 185 g/eq was
prepared according to the literature [12]. Pd/C (10 wt%), hydrochloric 2.5. Preparation of epoxy thermosets
acid (12 mol/L), sodium hydroxide (NaOH), epichlorohydrin (ECH),
acetone, dichloromethane (DCM), petroleum ether (PET, 60–90 ◦ C) and The epoxy resin, curing agent (MeTHPA, the molar ratio of MeTHPA
ethanol were purchased from Aladdin Reagent Co., Ltd. (Shanghai, to epoxy groups was 0.85:1) and DMBA (0.5% mass content of curing
China). Bisphenol A epoxy resin (DGEBA) with EEW of 196 g/eq was agent) were mixed completely at 90 ◦ C. Then the mixture was poured
provided by Nantong Xingchen Synthetic Material Co. Ltd. (Jiangsu, into a preheated Teflon mould and degassed in a vacuum oven at 90 ◦ C
China). Methyltetrahydrophthalic anhydride (MeTHPA) was provided
by Jiaxing Lianxin Chemical New Materials Co. Ltd. (Zhejiang, China). Table 1
31
Trimethylbenzenemethanaminium chloride (TEBAC), N,N-dime­ The content of hydroxyl groups based on P NMR spectra.
thylbenzylamine (DMBA), deuterated chloroform (CDCl3), pyridine and Alkali DL1 DL2 DL3 DL4
2-chloro-4,4,5,5-tetramethyi-1,3,2-dioxaphospholane (TMDP) were lignin

purchased from Tansoole Reagent Co., Ltd. (Shanghai, China). Mn (g/mol) 2437 1451 1137 836 1725
Hydrogen (99.99%) was commercially available. All chemical reagents Yield (wt%) – 90 89 87 –
Insoluble fractions (wt 87 84 78 100
were used without further purification. –
%)
Aliphatic OH (mmol/g) 0.60 0.37 1.13 1.39 0.47
2.2. Preparation of lignin Syringyl OH (mmol/g) 1.69 1.88 1.64 1.70 1.77
Guaiacyl OH (mmol/g) 0.85 1.77 1.69 1.62 1.68
The alkali lignin (from Poplar) was extracted from paper black liquor p-Hydroxyphenyl OH 0.05 0.65 0.65 0.73 0.58
(mmol/g)
by acid-precipitation method. Hydrochloric acid (12 mol/L) was added Carboxylic acid OH 0.07 0.06 0.06 0.003 0.06
dropwise into the black liquor until the pH of solution was 2–3. The (mmol/g)
precipitated lignin was filtered, and then washed with distilled water to Phenolic OH (mmol/g) 2.59 4.30 3.98 4.05 4.03
pH 7 and dried at 60 ◦ C for 24 h. Finally, the obtained solid was ground Total OH (mmol/g) 3.26 4.73 5.17 5.44 4.56
to powder. The purity, molecular weight, total content of hydroxyl DLs were extracted with DCM/PET solution (VDCM/VPET = 1:3) to generate
groups and the content of phenolic hydroxyl groups of alkali lignin was insoluble fractions (oligomer-rich fraction) and soluble fractions (monomer-rich
98%, 2437 g/mol, 3.26 mmol/g and 2.59 mmol/g, respectively. fraction); DL4: insoluble fractions of DL1.

1401
G. Liu et al. International Journal of Biological Macromolecules 193 (2021) 1400–1408

for at least 10 min. After that, the mixture was cured at 120 ◦ C for 4 h, China) was used to measure the tensile and flexural properties of the
160 ◦ C for 4 h and 180 ◦ C for 4 h. For comparison, commercial bisphenol cured products at room temperature (25 ◦ C) according to China National
A epoxy resin (DGEBA) was also cured under the same conditions. The Standard GB/T 1040.1-2006 and GB/T 9341-2000, respectively. Impact
dosage of MeTHPA for epoxy prepolymer was calculated as the strength of the cured products were measured using a XJJY-5 impact test
following Eq. (1): machine (Chengde, China) at room temperature (25 ◦ C) according to
China National Standard GB/T 1043.1-2008. The rectangular shaped
mepoxy × MMeTHPA × 0.85
mMeTHPA = (1) samples (100 mm × 10 mm × 4 mm) were used for flexural and impact
EEW
strength tests, and the samples with dumbbell shape (100 mm × 5 mm ×
mMeTHPA: amount of MeTHPA (g); mepoxy: amount of epoxy prepol­ 4 mm) were used for tensile strength tests. Average values were calcu­
ymer (g); MMeTHPA: the molar mass of MeTHPA (g/mol); EEW: EEW of lated at least 10 specimens.
epoxy prepolymer (g/eq). The composition of the mixtures were sum­
marized in Table 2. 2.7. Crosslinking density

2.6. Characterization The crosslinking densities of the cured products were investigated by
DMA. The storage modulus E′ in the rubbery plateau was used to
The FT-IR spectra were recorded on ALPHAIIFT-IR spectrophotom­ calculate the crosslinking density as described in the following Eq. (2)
eter (Bruker, Switzerland). The 1H NMR, 13C NMR and 31P NMR spectra [52,53]:
were carried out to demonstrate the chemical structures of samples on E'
BloSpin AG 400 MHz spectrometer (Bruker, Switzerland), chemical ve = (2)
3RT
shifts were given with respect to CHCl3/CDCl3 (δ 1H = 7.27, δ 13C =
77.0). The 31P NMR of alkali lignin and its depolymerized products were where R was the gas constant (8.31 J mol− 1 K− 1), T (Tα + 30 ◦ C) was the
prepared and analyzed according to the literatures [49,50]. The vis­ temperature in Kelvin and E′ was the storage modulus at corresponding
cosities were measured by a Brookfield DV-S rotational viscometer. The temperature, Tα was the α-relaxation temperature taken as the peak
molecular weight of samples were determined by gel permeation chro­ maximum from the tan δ curve.
matography (GPC, Agilent 1100 series, Agilent, USA). Polystyrene with
the molecular weight range of 162–3000 g/mol was used as a calibration 2.8. Gel content
standard. The EEW of lignin-based epoxy resins were determined by
hydrochloric acid–acetone method [51]. Differential scanning calorim­ The cured products with known weight (W1) were immersed in
etry (DSC) thermograms were recorded with PerkinElmer Diamond tetrahydrofuran (THF) at room temperature for 24 h. Afterwards the
differential scanning calorimeter (USA) at a heating rate of 20 ◦ C/min samples were dried in an oven at 100 ◦ C for 24 h and weighed again
under a N2 atmosphere (20 mL/min flow rate). Thermogravimetric an­ (W2). Gel content (GC) was calculated according to the following Eq. (3)
alyses (TGA) were performed with NETZSCH STA 409 PC/PG ther­ [54]. The results were reported as the mean of triplicate experiments.
mogravimetric analyzer (Germany) at a heating rate of 10 ◦ C/min under
W2
a nitrogen atmosphere. Dynamic mechanical analyses (DMA) were GC = (3)
carried out on a Q800 dynamic mechanical analyzer (TA instrument, W1
USA) at a frequency of 1 Hz, temperature from − 10 ◦ C to 200 ◦ C, and
heating rate of 3 ◦ C/min. The tests were conducted using the dual 3. Results and discussion
cantilever mode, and the size of the samples was about 60 mm × 10 mm
× 4 mm. A universal testing machine (CMT4304, Shenzhen SANS, 3.1. Preparation and characterization of lignin and its depolymerized
products
Table 2
Composition of the mixtures.
The reductive depolymerization of lignin, which was usually con­
ducted in the presence of hydrogenation catalyst under a pressurized
LEP ECGE EEW Epoxy MeTHPA DMBA
hydrogen atmosphere, has been considered as a promising method for
(g) (g) (g/eq) groups (g) (mg)
(mmol) obtaining lignin oligomers with more reactive functional groups, higher
reactivity and better solvent solubility [38–41,55]. In this work, to es­
LEP(1)/ 20 0 313 64 9 45
MeTHPA
timate the effects of the degree of lignin depolymerization on the
LEP(2)/ 20 0 313 64 9 45 physical and chemical properties of LEPs, Pd/C was employed to cata­
MeTHPA lyze alkali lignin to oligomers with lower molecular weight and more
LEP(3)/ 20 0 313 64 9 45 reactive phenolic hydroxyl groups. The chemical structures of alkali
MeTHPA
lignin and its depolymerized products were characterized by FT-IR
LEP(4)/ 20 0 313 64 9 45
MeTHPA spectroscopy [56]. As shown in Fig. 1, the absorption peak intensities
LEP80/ 16 4 275 73 10 50 of –OH groups (at about 3360 cm− 1) in the spectra of DLs were higher
ECGE20/ than that of alkali lignin, which indicated that the content of hydroxyl
MeTHPA groups in lignin was improved. The absorption peaks at about 2930
LEP60/ 12 8 245 82 12 60
ECGE40/
cm− 1 were supposed to represent the C–H stretching in methoxyl,
MeTHPA methyl and methylene groups of the side chains. The absorption peaks at
LEP40/ 8 12 221 90 13 65 about 1710 cm− 1 were attributed to the carbonyl groups of the alkali
ECGE60/ lignin and DLs. Especially, the absorption peaks observed at about 1600
MeTHPA
cm− 1, 1515 cm− 1 and 1455 cm− 1 were assigned to the aromatic ring
LEP20/ 4 16 202 99 14 70
ECGE80/ stretching mode of phenyl-propane skeleton, which indicated that the
MeTHPA basic skeleton of lignin was not changed during the reductive depoly­
ECGE/ 0 20 185 108 15 75 merization reactions [57]. The absorption peaks at about 1265 cm− 1,
MeTHPA 1100 cm− 1 and 820 cm− 1 represented guaiacyl units (G), syringyl units
LEP(4) was blended with ECGE and cured with MeTHPA to form LEP/ECGE/ (S) and p-hydroxyphenyl (H) units, respectively, which confirmed that
MeTHPA thermosets. all of the samples belonged to GHS lignin [58].

1402
G. Liu et al. International Journal of Biological Macromolecules 193 (2021) 1400–1408

Fig. 1. FT-IR spectra of alkali lignin and its depolymerized products. Fig. 2. FT-IR spectra of lignin-based epoxy resins.

The 31P NMR spectra were also analyzed to speculate the structure the 13C NMR of the LEPs (Fig. 3), which were assigned to the CH and CH2
changes and the quantification of reactive hydroxyl functionalities in of epoxy groups, respectively, also confirmed the successful formation of
alkali lignin and DLs (Fig. S1) [49,50]. The assignments of signals for LEPs.
aliphatic, guaiacylic, syringylic, p-hydroxyphenyl and carboxylic OH To explore the thermal and mechanical properties of the resulting
groups were shown in Table 1. Compared with alkali lignin, the content polymers, MeTHPA was selected to react with the epoxy resins to form
of phenolic hydroxyl groups and the total content of hydroxyl groups in cross-linked epoxy thermosets (Scheme 2). The chemical structures of
DLs increased obviously, indicating that the hydrogenolysis processes the epoxy thermosets were characterized by FT-IR. Taking LEP(4)/
were very effective to increase the reactivity of alkali lignin. Further­ MeTHPA and LEP80/ECGE20/MeTHPA cured products for example
more, compared with the relative content of S, G and H units in alkali (Fig. 4), compared with the FT-IR spectra of epoxy resin prepolymers,
lignin, the relative content of S units in DLs decreased, but the relative the disappearance of the epoxy groups at 907 cm− 1 and the increase of
content of G and H units in DLs increased significantly, which suggested characteristic absorption peaks around 1727 cm− 1 due to the C– –O
that S units were more prone to be damaged during the reductive stretching of the carbonyl groups, which confirmed that the epoxy
depolymerization of alkali lignin. groups were completely reacted with MeTHPA to form epoxy networks
(Fig. 5).
3.2. Synthesis and characterization of lignin-based epoxy resins
3.3. Thermal properties of the epoxy thermosets
A series of LEPs were prepared by the reaction of phenolic hydroxyl
groups of DLs with epichlorohydrin under the catalysis of TEBAC The glass transition temperatures (Tg) of the epoxy thermosets were
(Scheme 1). The chemical structures of the obtained epoxy resins were measured by DSC analysis. As illustrated in Fig. 6, the LEP/MeTHPA
determined by FT-IR, 1H NMR and 13C NMR. As shown in Fig. 2, thermosets had lower Tg than DGEBA/MeTHPA thermoset. Because the
compared with the FT-IR spectra of DLs, the structural integrity of the aliphatic side chain of lignin made the motion of macromolecular
lignin skeleton was preserved in LEPs, as well as the peak intensities of backbone easily [31]. Moreover, the Tg of the LEP/MeTHPA thermosets
–OH groups (absorbance at about 3360 cm− 1) decreased and the were influenced by the degree of lignin depolymerization, as the degree
characteristic absorption peaks of epoxy groups at 907 cm− 1 were of lignin depolymerization increased, the Tg of the LEP/MeTHPA ther­
appeared evidently, which suggested that the epoxy groups had been mosets decreased. Compared to LEP(2)/MeTHPA and LEP(3)/MeTHPA
introduced into the lignin units expectably [59]. Additionally, the cured products, LEP(1)/MeTHPA cured product had the highest Tg,
characteristic signals at 3.67–3.86 ppm and 2.61–2.83 ppm in the 1H which could be attributed to its highest crosslinking density (Table 3).
NMR of LEPs, as well as the characteristic signals at 44.6–56.0 ppm in Furthermore, among DL1, DL2 and DL3, DL1 had the highest content of

Scheme 1. Preparation of lignin-based epoxy resins

1403
G. Liu et al. International Journal of Biological Macromolecules 193 (2021) 1400–1408

Fig. 3. 1H NMR and 13

C NMR spectra of lignin-based epoxy resin.

Scheme 2. Formation of epoxy thermosets

oligomer-rich fractions (Table 1), these rigid structures also help to in­ separation occurred. Especially, in LEP/ECGE/MeTHPA curing systems,
crease the Tg of the LEP(1)/MeTHPA thermoset. To confirm the effects of the ECGE was well compatible with LEPs.
monomer-rich fractions on the properties of LEPs, DL1 was purified by The thermal stabilities of the epoxy thermosets were investigated by
solvent extraction to give oligomer-rich fractions DL4, which was used TGA under nitrogen atmosphere (Fig. 7). The temperatures at 5% of
to prepare LEP(4). Compared LEP(4)/MeTHPA to LEP(1)/MeTHPA weight loss (Td) were presented in Tables 3 and 4. The addition of ECGE
curing system, the Tg of the cured product was improved obviously by did not have obvious influence on their thermal stabilities, and the Td of
the extraction of monomer-rich fractions from DL1, indicating that the the cured products were all above 320 ◦ C, indicating that all the epoxy
Tg of the epoxy thermosets decreased with the increase of monomer-rich thermosets had good thermal-resistance properties. Nevertheless, the Td
fractions in DLs. of the LEP/MeTHPA thermosets were lower than that of the DGEBA/
Compared to pristine LEPs, the ECGE modified epoxy thermosets MeTHPA thermoset. It was due to the labile groups of lignin, such as
displayed lower Tg and the Tg decreased with the increase of ECGE methoxy groups, ester bonds and ether bonds, which could get readily
content (Table 4). Because the crosslinking densities of epoxy thermo­ decomposed at lower temperature [43]. Furthermore, the degree of
sets were reduced with the addition of ECGE, as well as the long flexible lignin depolymerization also had a noticeable effect on the Td of the
aliphatic chains in ECGE facilitated the mobility of macromolecular LEP/MeTHPA thermosets, as the degree of lignin depolymerization
backbone. Notably, in the range of scanning temperature from − 20 ◦ C to increased, the Td of the LEP/MeTHPA thermosets decreased. Because the
150 ◦ C, there was only one Tg in each DSC curve, indicating that all the increase of the degree of lignin depolymerization could effectively
epoxy thermosets were homogeneous phase systems and no phase improve the content of monomer-rich fractions in DLs, which could

1404
G. Liu et al. International Journal of Biological Macromolecules 193 (2021) 1400–1408

maximum, corresponds to the main mechanical relaxation associated

with the glass transition of the polymers. As shown in Fig. 8a and b, the
narrow α-relaxation peak indicated that there was no phase separation
and the compatibility between ECGE and LEPs was good. Furthermore,
the Tα of the cured products were also influenced by the degree of lignin
depolymerization and the addition of ECGE. With the increase of the
degree of lignin depolymerization and the content of ECGE, the Tα of the
cured products decreased, which were in consistent with the Tg from
DSC analysis.
Variation trends of the E′ curves of the epoxy thermosets were given
in Fig. 8c and d. As shown in Fig. 8c and d, the E′ values of the epoxy
thermosets decreased with the increase of temperature, and a rapid
decrease of E′ could be observed when the temperature got close to Tα,
corresponding to the glass transition. At the temperature above the
respective Tα of a given sample, the E′ values of the epoxy thermosets
decreased with the increase of the degree of lignin depolymerization and
the content of ECGE in the curing systems, which was due to the
decrease of the crosslinking densities and the rigidity of segment
structures.
Fig. 4. FT-IR spectra of lignin-based epoxy thermosets.

reduce the crosslinking densities of the epoxy thermosets and get readily 3.5. Mechanical properties of epoxy thermosets
decomposed at lower temperatures. Moreover, compared to LEP(1)/
MeTHPA curing system, the Td of LEP(4)/MeTHPA thermoset was also Tensile, flexural and impact strength tests were performed to eval­
improved by the extraction of monomer-rich fractions from DL1. These uate the mechanical properties of the epoxy thermosets (Fig. 9). Typical
results confirmed that the monomer-rich fractions in DLs played an parameters were summarized in Tables 3 and 4. As shown in Tables 3
important role in reducing the Td of epoxy thermosets. and 4, the tensile, flexural and impact strength of LEP/MeTHPA ther­
mosets decreased with the increase of the degree of lignin depolymer­
3.4. Dynamic mechanical analysis ization. This could be attributed to the decrease of their crosslinking
densities, as well as the decrease of the content of oligomer-rich frac­
DMA was employed to determine the effects of lignin depolymer­ tions in DLs, which rigid structures could help to enhance the mechan­
ization and the content of ECGE on the dynamic mechanical properties ical properties of the epoxy thermosets [40]. Compared LEP(1)/
of the epoxy thermosets. The storage modulus (E′ ) and the loss factor MeTHPA to LEP(4)/MeTHPA curing system, the mechanical properties
(tan δ) as a function of temperature were shown in Fig. 8, and the cor­ of the epoxy thermoset were improved obviously by the extraction of
responding data were summarized in Tables 3 and 4. The α-relaxation monomer-rich fractions from DL1, the tensile, flexural and impact
temperature (Tα), temperature at which tan δ passed through the strength of the cured product reached 60 MPa, 106 MPa and 11 kJ/m2,

Fig. 5. Reactions of epoxy group with anhydride.

Fig. 6. DSC curves of the epoxy thermosets.

1405
G. Liu et al. International Journal of Biological Macromolecules 193 (2021) 1400–1408

Table 3
Properties of the LEPs and LEP/MeTHPA thermosets.
Epoxy resins Yield Viscosity EEW Tg (◦ C) Td (◦ C) Tα (◦ C) E′ Tensile strength Flexural strength Impact strength νe GC
(wt%) (mPa⋅s) (g/eq) (MPa) (MPa) (MPa) (kJ/m2) (mol/m3) (%)

LEP(1) 90 24,500 313 98 328 114 11 59 ± 2 86 ± 4 10 1034 99

(90 ◦ C)
LEP(2) 88 15,200 313 83 323 100 7 57 ± 3 75 ± 3 10 699 98
(90 ◦ C)
LEP(3) 88 4650 313 78 320 98 7 47 ± 4 61 ± 5 9 697 98
(90 ◦ C)
LEP(4) 87 Ð 313 104 335 128 22 60 ± 4 106 ± 4 11 2028 99
DGEBA – 12,300 196 128 362 ND ND 74 ± 3 112 ± 2 15 ND 99
(25 ◦ C)

LEP(1): derived from DL1; LEP(2): derived from DL2; LEP(3): derived from DL3; LEP(4): derived from DL4; E′ : storage modulus at Tα + 30 ◦ C; νe: crosslinking density;
GC: Gel content; Ð: can't detected at 90 ◦ C; ND: not detected.

Table 4
Properties of the LEP/ECGE/MeTHPA thermosets.
Epoxy resins Viscosity Tg (◦ C) Td (◦ C) Tα E′ Tensile strength Flexural strength Impact strength νe GC
(mPa⋅s) (◦ C) (MPa) (MPa) (MPa) (kJ/m2) (mol/m3) (%)

LEP80/ECGE20 2659 97 323 112 19 77 ± 5 115 ± 4 14 1834 99

(90 ◦ C)
LEP60/ECGE40 640 89 334 97 18 75 ± 3 103 ± 3 14 1790 99
(90 ◦ C)
LEP40/ECGE60 230 65 322 85 17 72 ± 2 94 ± 3 13 1787 98
(90 ◦ C)
LEP20/ECGE80 160 59 324 70 13 65 ± 1 76 ± 3 14 1354 99
(90 ◦ C)
ECGE 93 55 321 63 9 54 ± 2 43 ± 2 14 953 99
(25 ◦ C)

LEP: LEP(4); E′ : storage modulus at Tα + 30 ◦ C; νe: crosslinking density (mol/m3); GC: Gel content.

Fig. 7. TG curves of the epoxy thermosets.

respectively. 4. Conclusions
Notably, the addition of ECGE also had a remarkable positive effect
on mechanical properties of the cured products. The tensile, flexural and A series of lignin-based epoxy resins (LEPs) were successfully syn­
impact strength of the epoxy thermosets increased first with the increase thesized from lignin oligomers derived from partial reductive depoly­
of ECGE dosage. The epoxy thermoset with 20 wt% ECGE loadings merization of alkali lignin. The LEP/MeTHPA thermosets exhibited good
exhibited the best toughening effect, the tensile, flexural and impact thermal and mechanical properties. Especially, by separating monomer-
strength of the cured product reached its maximum value of 77 MPa, rich fractions from DL, the Tg and thermal stability of the cured product
115 MPa and 14 kJ/m2, respectively, which were comparable to those of were obviously improved, as well as the tensile, flexural and impact
DGEBA/MeTHPA thermoset. Because the internal stress of the polymers strength of the cured product were found up to be 60 MPa, 106 MPa and
decreased by introducing ECGE into the epoxy networks [60]. When the 11 kJ/m2, respectively. Furthermore, the incorporation of ECGE into
content of ECGE exceeded 20 wt%, the tensile and flexural strength of epoxy networks also had a remarkable positive effect on mechanical
the epoxy thermosets decreased evidently, which could be attributed to properties of the cured products. The epoxy thermoset with 20 wt%
the reduction of crosslinking densities and the increase of flexible ECGE had the best toughening effect, the tensile, flexural and impact
segments. strength of the cured product reached its maximum value of 77 MPa,
115 MPa and 14 kJ/m2, respectively, indicating that the bio-based

1406
G. Liu et al. International Journal of Biological Macromolecules 193 (2021) 1400–1408

Fig. 8. Tan δ versus temperature (a) and (b) for the epoxy thermosets; Storage modulus (E′ ) versus temperature (c) and (d) for the epoxy thermosets.

Acknowledgments

This work was supported by the National Natural Science Foundation

of China (31890774, 31890770) and the National Key Research and
Development Program of China (2017YFD0601003).

Appendix A. Supplementary data

Supplementary data to this article can be found online at https://doi.

org/10.1016/j.ijbiomac.2021.10.203.

References

[1] S.Q. Ma, D.C. Webster, Degradable thermosets based on labile bonds or linkages: a
review, Prog. Polym. Sci. 76 (2018) 65–110.
[2] Y. Tian, Q. Wang, L. Shen, Z. Cui, L. Kou, J. Cheng, J. Zhang, A renewable
resveratrol-based epoxy resin with high tg, excellent mechanical properties and
low flammability, Chem. Eng. J. 383 (2020), 123124.
[3] Y. Tao, L. Fang, M. Dai, C. Wang, J. Sun, Q. Fang, Sustainable alternative to
bisphenol a epoxy resin: high-performance recyclable epoxy vitrimers derived from
Fig. 9. Stress–strain curves of LEP/MeTHPA and LEP/ECGE/ protocatechuic acid, Polym. Chem. 11 (27) (2020) 4500–4506.
[4] F. Liguori, C. Moreno-Marrodan, P. Barbaro, Biomass-derived chemical substitutes
MeTHPA thermosets. for bisphenol a: recent advancements in catalytic synthesis, Chem. Soc. Rev. 49
(17) (2020) 6329–6363.
epoxy resin from lignin oligomers and cardanol could be a promising [5] R. Auvergne, S. Caillol, G. David, B. Boutevin, J.P. Pascault, Biobased
thermosetting epoxy: present and future, Chem. Rev. 114 (2) (2014) 1082–1115.
candidate for BPA epoxy resin. [6] J. Wan, J. Zhao, X. Zhang, H. Fan, J. Zhang, D. Hu, P. Jin, D.Y. Wang, Epoxy
thermosets and materials derived from bio-based monomeric phenols:
Declaration of competing interest transformations and performances, Prog. Polym. Sci. 108 (2020), 101287.
[7] C. Zhang, T.F. Garrison, S.A. Madbouly, M.R. Kessler, Recent advances in vegetable
oil-based polymers and their composites, Prog. Polym. Sci. 71 (2017) 91–143.
The authors declare no competing financial interests. [8] J. Liu, S. Wang, Y. Peng, J. Zhu, W. Zhao, X. Liu, Advances in sustainable
thermosetting resins: from renewable feedstock to high performance and
recyclability, Prog. Polym. Sci. 113 (2021), 101353.

1407
G. Liu et al. International Journal of Biological Macromolecules 193 (2021) 1400–1408

[9] F. Ng, G. Couture, C. Philippe, B. Boutevin, S. Caillol, Bio-based aromatic epoxy [36] H. Yang, B. Yu, X. Xu, S. Bourbigot, H. Wang, P. Song, Lignin-derived bio-based
monomers for thermoset materials, Molecules 22 (1) (2017) 149. flame retardants toward high-performance sustainable polymeric materials, Green
[10] C. Di Mauro, S. Malburet, A. Genua, A. Graillot, A. Mija, Sustainable series of new Chem. 22 (7) (2020) 2129–2161.
epoxidized vegetable oil-based thermosets with chemical recycling properties, [37] W. Liu, C. Fang, F. Chen, X. Qiu, Strong, reusable and self-healing lignin-containing
Biomacromolecules 21 (9) (2020) 3923–3935. polyurea adhesives, ChemSusChem 13 (17) (2018) 4691–4701.
[11] M.D. Garrison, M.A. Savolainen, A.P. Chafin, J.E. Baca, A.M. Bons, B.G. Harvey, [38] C. Li, X. Zhao, A. Wang, G.W. Huber, T. Zhang, Catalytic transformation of lignin
Synthesis and characterization of high-performance, bio-based epoxy-amine for the production of chemicals and fuels, Chem. Rev. 115 (21) (2015)
networks derived from resveratrol, ACS Sustain. Chem. Eng. 8 (37) (2020) 11559–11624.
14137–14149. [39] W. Schutyser, T. Renders, S.V.D. Bosch, S.F. Koelewijn, G.T. Beckham, B.F. Sels,
[12] J. Chen, X. Nie, Z. Liu, Z. Mi, Y. Zhou, Synthesis and application of polyepoxide Chemicals from lignin: an interplay of lignocellulose fractionation,
cardanol glycidyl ether as biobased polyepoxide reactive diluent for epoxy resin, depolymerisation, and upgrading, Chem. Soc. Rev. 47 (3) (2018) 852–908.
ACS Sustain. Chem. Eng. 3 (6) (2015) 1164–1171. [40] Y.M. Questell-Santiago, M.V. Galkin, K. Barta, J.S. Luterbacher, Stabilization
[13] S. Benyahya, C. Aouf, S. Caillol, B. Boutevin, J.P. Pascault, H. Fulcrand, strategies in biomass depolymerization using chemical functionalization, Nat. Rev.
Functionalized green tea tannins as phenolic prepolymers for bio-based epoxy Chem. 4 (6) (2020) 311–330.
resins, Ind. Crop. Prod. 53 (2014) 296–307. [41] Y. Li, S.D. Karlen, B. Demir, H. Kim, J. Luterbacher, J.A. Dumesic, S.S. Stahl,
[14] C. Gioia, M. Colonna, A. Tagami, L. Medina, O. Sevastyanova, L.A. Berglund, J. Ralph, Mechanistic study of diaryl ether bond cleavage during palladium-
M. Lawoko, Lignin-based epoxy resins: unravelling the relationship between catalyzed lignin hydrogenolysis, ChemSusChem 13 (17) (2020) 4487–4494.
structure and material properties, Biomacromolecules 21 (5) (2020) 1920–1928. [42] H. Sun, G. Wang, J. Ge, N. Wei, W. Li, W. Sui, A.M. Parvez, C. Si, Reduction of
[15] C.H. Chen, S.H. Tung, R.J. Jeng, M.M. Abu-Omar, C.H. Lin, A facile strategy to lignin heterogeneity using aqueous two-phase system: a facile and universal “one-
achieve fully bio-based epoxy thermosets from eugenol, Green Chem. 21 (16) step-three-fractions” approach, Int. J. Biol. Macromol. 186 (2021) 341–350.
(2019) 4475–4488. [43] E. Feghali, D.J.V.D. Pas, K.M. Torr, Towards bio-based epoxy thermoset polymers
[16] K.H. Nicastro, C.J. Kloxin, T.H. Epps, Potential lignin-derived alternatives to from depolymerized native lignins produced at pilot scale, Biomacromolecules 21
bisphenol a in diamine hardened epoxy resins, ACS Sustain. Chem. Eng. 6 (11) (4) (2020) 1548–1559.
(2018) 14812–14819. [44] E. Feghali, D.J.V.D. Pas, A.J. Parrott, K.M. Torr, Biobased epoxy thermoset
[17] J. Liu, J. Dai, S. Wang, Y. Peng, L. Cao, X. Liu, Facile synthesis of bio-based reactive polymers from depolymerized native hardwood lignin, ACS Macro Lett. 9 (8)
flame retardant from vanillin and guaiacol for epoxy resin, Compos. B. Eng. 190 (2020) 1155–1160.
(2020), 107926. [45] L.C. Over, E. Grau, S. Grelier, M.A.R. Meier, H. Cramail, Synthesis and
[18] J. Meng, Y. Zeng, G. Zhu, J. Zhang, P. Chen, Y. Cheng, Z. Fang, K. Guo, Sustainable characterization of epoxy thermosetting polymers from glycidylated organosolv
bio-based furan epoxy resin with flame retardancy, Polym. Chem. 10 (19) (2019) lignin and bisphenol a, Macromol. Chem. Phy. 218 (8) (2017) 1600411.
2370–2375. [46] J. Xin, M. Li, R. Li, M.P. Wolcott, J. Zhang, Green epoxy resin system based on
[19] Z. Wang, L. Yuan, M.S. Ganewatta, M.E. Lamm, M.A. Rahman, J. Wang, S. Liu, lignin and tung oil and its application in epoxy asphalt, ACS Sustain. Chem. Eng. 4
C. Tang, Plant oil-derived epoxy polymers toward sustainable biobased thermosets, (5) (2016) 2754–2761.
Macromol. Rapid. Comm. 38 (11) (2017) 1700009. [47] F. Ferdosian, Z. Yuan, M. Anderson, C.C. Xu, Synthesis and characterization of
[20] M. Fache, E. Darroman, V. Besse, R. Auvergne, S. Caillol, B. Boutevin, Vanillin, a hydrolysis lignin-based epoxy resins, Ind. Crop. Prod. 91 (2016) 295–301.
promising biobased building-block for monomer synthesis, Green Chem. 16 (4) [48] F. Ferdosian, Y. Zhang, Z. Yuan, M. Anderson, C.C. Xu, Curing kinetics and
(2014) 1987–1998. mechanical properties of bio-based epoxy composites comprising lignin-based
[21] A. Arbenz, L. Avérous, Chemical modification of tannins to elaborate aromatic epoxy resins, Eur. Polym. J. 82 (2016) 153–165.
biobased macromolecular architectures, Green Chem. 17 (5) (2015) 2626–2646. [49] R.C. Sun, Lignin source and structural characterization, ChemSusChem 13 (17)
[22] Z. Sun, B. Fridrich, A.D. Santi, S. Elangovan, K. Barta, Bright side of lignin (2020) 4385–4393.
depolymerization: toward new platform chemicals, Chem. Rev. 118 (2) (2018) [50] X. Meng, C. Crestini, H. Ben, N. Hao, Y. Pu, A.J. Ragauskas, D.S. Argyropoulos,
614–678. Determination of hydroxyl groups in biorefinery resources via quantitative 31P
[23] B.M. Upton, A.M. Kasko, Strategies for the conversion of lignin to high-value NMR spectroscopy, Nat. Protoc. 14 (9) (2019) 2627–2647.
polymeric materials: review and perspective, Chem. Rev. 116 (4) (2016) [51] G.F. Liu, G.M. Wu, J. Chen, S.P. Huo, C. Jin, Z.W. Kong, Synthesis and properties of
2275–2306. POSS-containing gallic acid-based non-isocyanate polyurethanes coatings, Polym.
[24] S. Nikafshar, J. Wang, K. Dunne, P. Sangthonganotai, M. Nejad, Choosing the right Degrad. Stabil. 121 (2015) 247–252.
lignin to fully replace bisphenol a in epoxy resin formulation, ChemSusChem 14 (4) [52] G.X.D. Hoe, M.T. Zumstein, B.J. Tiegs, J.P. Brutman, K. Mcneill, M. Sander, G.
(2021) 1184–1195. W. Coates, M.A. Hillmyer, Sustainable polyester elastomers from lactones:
[25] X. Zhen, H. Li, Z. Xu, Q. Wang, S. Zhu, Z. Wang, Z. Yuan, Facile synthesis of lignin- synthesis, properties, and enzymatic hydrolyzability, J. Am. Chem. Soc. 140 (3)
based epoxy resins with excellent thermal-mechanical performance, Int. J. Biol. (2018) 963–973.
Macromol. 182 (2021) 276–285. [53] S.W. Shao, C.H. Chen, J.R. Chan, T.Y. Juang, M.M. Abu-Omar, C.H. Lin, Full atom-
[26] J. Sternberg, O. Sequerth, S. Pilla, Green chemistry design in polymers derived efficiency transformation of wasted polycarbonates into epoxy thermosets and the
from lignin: review and perspective, Prog. Polym. Sci. 113 (2021), 101344. catalyst-free degradation of the thermosets for environmental sustainability, Green
[27] D.J. van de Pas, K.M. Torr, Biobased epoxy resins from deconstructed native Chem. 22 (14) (2020) 4683–4696.
softwood lignin, Biomacromolecules 18 (8) (2017) 2640–2648. [54] A.S. Mora, R. Tayouo, B. Boutevin, G. David, S. Caillol, Vanillin-derived amines for
[28] C. Gioia, G.L. Re, M. Lawoko, L. Berglund, Tunable thermosetting epoxies based on bio-based thermosets, Green Chem. 20 (17) (2018) 4075–4084.
fractionated and well-characterized lignins, J. Am. Chem. Soc. 140 (11) (2018) [55] D. Tang, X. Huang, W. Tang, Y. Jin, Lignin-to-chemicals: application of catalytic
4054–4061. hydrogenolysis of lignin to produce phenols and terephthalic acid via metal-based
[29] S. Zhao, X. Huang, A.J. Whelton, M.M. Abu-Omar, Formaldehyde-free method for catalysts, Int. J. Biol. Macromol. 190 (2021) 72–85.
incorporating lignin into epoxy thermosets, ACS Sustain. Chem. Eng. 6 (8) (2018) [56] L.L. An, C.L. Si, J.H. Wang, G.H. Wang, W.J. Sui, Z.Y. Tao, Enhancing the solubility
10628–10636. and antioxidant activity of high-molecular-weight lignin by moderate
[30] P. Jędrzejczak, M.N. Collins, T. Jesionowski, Ł. Klapiszewski, The role of lignin and depolymerization via in situ ethanol/acid catalysis, Ind. Crop. Prod. 128 (2019)
lignin-based materials in sustainable construction—A comprehensive review, Int. 177–185.
J. Biol. Macromol. 187 (2021) 624–650. [57] Y. Cao, S.S. Chen, D.C.W. Tsang, J.H. Clark, V.L. Budarin, C. Hu, K.W. Wu,
[31] M. Culebras, M. Pishnamazi, G.M. Walker, M.N. Collins, Facile tailoring of S. Zhang, Microwave-assisted depolymerization of various types of waste lignins
structures for controlled release of paracetamol from sustainable lignin derived over two-dimensional CuO/BCN catalysts, Green Chem. 22 (3) (2020) 725–736.
platforms, Molecules 26 (6) (2021) 1593. [58] M. Brahim, N. Boussetta, N. Grimi, E. Vorobiev, I. Zieger-Devin, N. Brosse,
[32] A. Beaucamp, M. Culebras, M.N. Collins, Sustainable mesoporous carbon Pretreatment optimization from rapeseed straw and lignin characterization, Ind.
nanostructures derived from lignin for early detection of glucose, Green Chem. 23 Crop. Prod. 95 (2017) 643–650.
(15) (2021) 5696–5705. [59] S. Zhao, M.M. Abu-Omar, Renewable epoxy networks derived from lignin-based
[33] M. Culebras, A. Barrett, M. Pishnamazi, G.M. Walker, M.N. Collins, Wood-derived monomers: effect of cross-linking density, ACS Sustain. Chem. Eng. 4 (11) (2016)
hydrogels as a platform for drug-release systems, ACS Sustain. Chem. Eng. 9 (6) 6082–6089.
(2021) 2515–2522. [60] B. Wang, S. Ma, Q. Li, H. Zhang, J. Liu, R. Wang, Z. Chen, X. Xu, S. Wang, N. Lu,
[34] A. Jablonskis, A. Arshanitsa, A. Arnautov, G. Telysheva, D. Evtuguin, Evaluation of Y. Liu, S. Yan, J. Zhu, Facile synthesis of “digestible”, rigid-and-flexible, bio-based
ligno Boost™ softwood Kraft lignin epoxidation as an approach for its application building block for high-performance degradable thermosetting plastics, Green
in cured epoxy resins, Ind. Crop. Prod. 112 (2018) 225–235. Chem. 22 (4) (2020) 1275–1290.
[35] S. Zhang, T. Liu, C. Hao, L. Wang, J. Han, H. Liu, J. Zhang, Preparation of a lignin-
based vitrimer material and its potential use for recoverable adhesive, Green Chem.
20 (13) (2018) 2995–3000.

1408