Article
pubs.acs.org/Biomac
Biobased Epoxy Resins from Deconstructed Native Softwood Lignin
Daniel J. van de Pas* and Kirk M. Torr
Scion, Private Bag 3020, Rotorua 3046, New Zealand
ABSTRACT: The synthesis of novel epoxy resins from lignin
hydrogenolysis products is reported. Native lignin in pine
wood was depolymerized by mild hydrogenolysis to give an oil
product that was reacted with epichlorohydrin to give epoxy
prepolymers. These were blended with bisphenol A diglycidyl
ether or glycerol diglycidyl ether and cured with diethylenetri-
amine or isophorone diamine. The key novelty of this work
lies in using the inherent properties of the native lignin in
preparing new biobased epoxy resins. The lignin-derived epoxy
prepolymers could be used to replace 25−75% of the
bisphenol A diglycidyl ether equivalent, leading to increases of up to 52% in the flexural modulus and up to 38% in the
flexural strength. Improvements in the flexural strength were attributed to the oligomeric products present in the lignin
hydrogenolysis oil. These results indicate lignin hydrogenolysis products have potential as sustainable biobased polyols in the
synthesis of high performance epoxy resins.
■ INTRODUCTION
With the growth of the biobased economy, the chemical sector
is increasingly looking toward using biomass-derived molecules
and materials with new functionality, enhanced performance
attributes, and low carbon footprints. This has fueled interest in
replacing nonrenewable polymers, or components thereof, with
sustainable alternatives. Significant advances have been made in
developing both biobased thermoplastics1,2 and thermosets.3
For thermosets, aromatic intermediates are favored for their
structural rigidity as they impart desirable mechanical and
thermal properties to the material.4−6 The availability of
petroleum-derived aromatic compounds could decline in the
future as petrochemical feedstocks shift away from traditional
crude oil to shale gas and lighter tight oils that contain less
aromatics.7
Epoxy resins represent a major class of thermosetting resins
that demand a higher price than other polymers. Epoxy resins
are versatile thermosets because they can be combined with a
wide range of curing agents. This enables them to be tailored to
suit a diverse range of applications such as coatings, adhesives,
composites, and electrical encapsulation.8 The most commonly
used epoxy prepolymer is bisphenol A diglycidyl ether
(BADGE), which is commercially produced from bisphenol A
and epichlorohydrin. While a commercial route exists for the
production of biobased epichlorohydrin,9 there is considerable
interest in replacing bisphenol A with biobased polyol
alternatives that are equally capable of delivering a high
performance resin. Alternatives for bisphenol A are also being
sought on health and environmental grounds as it is a known
endocrine disrupting compound that can potentially leach from
BADGE-based epoxy resins used in food applications.10
A number of biobased alternatives to bisphenol A have been
investigated.3,9,11−13 Examples of biobased epoxy prepolymers
include epoxidized cardanol,14 and glycidylation products of
© 2017 American Chemical Society
isosorbide,15 gallic acid16 and lignin.4,6,17 Lignin is the only
renewable aromatic polymer that is available in larger quantities
at low cost that offers a potential source of ready-made
aromatic polyols. Lignin is a complex aromatic polymer derived
from p-coumaryl alcohol, coniferyl alcohol (G units), or sinapyl
alcohol (S units) building blocks, the proportions dictated by
the type of lignocellulosic species.18 The C9 phenylpropanoid
lignin units are linked together in the polymer by a variety of
different linkages, the most abundant being the β-O-4 ether
linkage.18 A number of strategies have been used for
incorporating lignin as a polyol precursor in epoxy resins.
Lignin can be blended and reacted with epoxy prepolymers
such as BADGE.6,19,20 Lignin can also be reacted with
epichlorohydrin to produce an epoxy prepolymer that can
then be cross-linked with curing agents.4,6 However, using
lignin directly can be challenging due to its poor solubility and
reactivity.21 Chemical modification of lignin (e.g., phenolation,
hydroxypropylation) has been effective in addressing these
limitations.4,6,17
In recent years there has been renewed interest in developing
epoxy resins from lignin.22−26 A new approach to producing
lignin-derived polyols is to depolymerize the lignin to lower
molecular weight compounds. There have been several reports
on producing epoxy resins from lignin model compounds.
Examples include vanillin and derivatives thereof,27−29 vanillyl
alcohol derivatives,30 phenol,31 isoeugenol,32 syringaresinol,33
and compounds based on propyl guaiacol and its demethylated
product.34−36 Model compounds are useful in assessing the
potential of lignin in materials applications, however it is
important that more structurally relevant and readily available
Received: June 1, 2017
Revised: July 4, 2017
Published: July 6, 2017
2640 DOI: 10.1021/acs.biomac.7b00767
Biomacromolecules 2017, 18, 2640−2648
Biomacromolecules
lignin streams be utilized in developing new polymers and
materials. Zhao and Abu-Omar (2017), for example, combined
demethylated lignin with a glycidylated derivative of
dihydroeugenol to produce lignin-containing epoxy resins.37
Processed lignins such as Kraft and organosolv lignins have
been depolymerized and used to produce epoxy resins.23,24,38,39
The chemical structures of processed lignins are often heavily
modified compared to native lignins due to depolymerization
(cleavage of C−O bonds) and repolymerization (formation of
C−C bonds) reactions that occur during extraction of the
lignin from biomass. Utilizing native lignin within biomass is an
important emerging strategy in the biorefinery concept. In this
approach, lignin is fractionated first from the lignocellulosic
matrix by catalytic upstream processing to produce a solvent-
soluble depolymerized lignin oil and a holocellulose-enriched
residue.18,40,41
We have previously reported that mild hydrogenolysis can
depolymerize lignin in situ in pine wood and an isolated native
lignin into a mixture of phenolic monomers, dimers and
oligomers.42,43 Mild hydrogenolysis selectively cleaves the β-O-
4 and α-O-4 ether linkages and stabilizes the lignin fragments
against repolymerization through catalytic reduction. In recent
years, there has been increased interest in lignin hydrogenolysis
as a pathway to valuable low molecular weight chemicals from
lignin.40,41,44−47 Most approaches use noble metal or Ni-based
catalysts and have focused on maximizing yields of monomeric
products. In this regard, lignins rich in S units and with high β-
O-4 contents, such as those found in hardwoods, are preferred.
Mild hydrogenolysis of softwood lignins, which are mainly
composed of G units, give lower yields of monomers and
higher yields of oligomeric products.40,42 Research on utilizing
hydrogenolysis products of native lignins to produce new
biobased materials is yet to be reported. In this study we
describe the development of novel biobased epoxy prepolymers
from hydrogenolysis products derived from softwood lignin and
their use as replacements for BADGE in new epoxy
thermosetting polymers. The novelty of this approach is that
it takes advantage of the inherent properties of the native lignin
in the wood before it is chemically altered as in conventional
wood pulping processes.
■ EXPERIMENTAL SECTION
Materials. Ground, dry, extractive-free Pinus radiata wood was
prepared as described previously.42 The Pd/C (5% Pd) catalyst,
epichlorohydrin, BADGE with an epoxy equivalent weight (EEW) of
174 g/mol, glycerol diglycidyl ether (GDGE) with an EEW of 143 g/
mol, phenyl glycidyl ether, diethylenetriamine (DETA), and
isophorone diamine (IPDA) were purchased from Sigma-Aldrich.
Hydrogenolysis. Hydrogenolysis reactions were carried out in a
450 mL limbo autoclave (Buchiglasuster, Switzerland) charged with
wood (12.9 g) and Pd/C (1.03 g, 8% w/w of wood) in dioxane/water
(1:1, 300 mL). The reactor was pressurized to 3.4 MPa with hydrogen
and heated to 195 °C for 24 h with stirring at 750 rpm.42 After cooling,
the contents of the reactor were filtered, extracted into dichloro-
methane and the extract was dried to constant weight to give the lignin
hydrogenolysis oil product (LH, 2.9 g). This product was fractionated
into a diethyl ether-insoluble fraction (LHO, ca. 50% (w/w)) and a
diethyl ether-soluble fraction.
Preparation of Lignin Hydrogenolysis Epoxy Prepolymer
(LHEP). The lignin hydrogenolysis product (8.22 g) was dissolved in
refluxing epichlorohydrin (13.7 mL). A 20% aqueous solution of
NaOH (1.40 g, 34.9 mmol) was added dropwise to the reaction
mixture over a 90 min period. During the reaction, water was removed
by azeotropic distillation with epichlorohydrin using a modified dean-
stark apparatus. The reaction was continued for a further 30 min,
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cooled, neutralized with phosphate buffer (pH 7.0, 0.3 M, 10 mL) and
excess epichlorohydrin was removed. The product was extracted into
dichloromethane, and the solvent was removed before dissolving in
dioxane and treating with 20% aqueous NaOH. The final product was
an amber-colored viscous oil (LHEP, ca. 88% yield w/w). The diethyl
ether-insoluble fraction of the lignin hydrogenolysis product (LHO)
was reacted in the same way to give the oligomeric lignin
hydrogenolysis epoxy prepolymer (LHOEP, ca. 84% yield w/w).
Chemical Analysis. Analysis of the hydrogenolysis products by
GCMS was performed as previously described.42 Gel permeation
chromatography was performed on a PSS SDV Lux 1000 Å column set
eluting with tetrahydrofuran using a Knauser Smartline GPC system
with UV detection at 254 nm. A calibration curve was constructed
using 4-n-propyl guaiacol, dihydro-diisoeugenol, and polystyrene
standards. 1H, 13C, 31P, and 2D HSQC NMR spectroscopy was
performed on a Bruker AVIII 400 MHz spectrometer equipped with a
BBO 5 mm probe. Hydroxyl content was determined by quantitative
31
P NMR spectroscopy as described previously.43 The EEW of the
epoxy resins was determined by potentiometric titration following
ASTM Standard D1652−04 scaled down to analyze 20 mg samples.
Total chlorine content was determined by the Campbell Micro-
analytical Lab (Otago University, New Zealand).48 Hydrolyzable
chlorine content was determined by titration following ASTM
Standard D1726−03 scaled down to analyze 25−50 mg samples.
The viscosity of the products, as 40% solutions in diethylene glycol
butyl ether, were measured at 25 °C using a Brookfield cone and plate
viscometer.
Preparation of Cured Epoxy Specimens. LHEP or LHOEP
were mixed with BADGE or GDGE in the desired proportions to give
a total mass of 0.6 g. Phenyl glycidyl ether (60 mg) was added as a
reactive diluent to all mixtures, unless indicated otherwise, and the
components were mixed thoroughly with warming to about 40 °C.
The EEW of the individual epoxy resin components was used to
calculate the equimolar amount of curing agent required to cure the
resin. The curing agent, either DETA or IPDA, was added and mixed
thoroughly before centrifuging at 4000 rpm for 1 min to remove air
bubbles. The mixture was warmed to about 40 °C and transferred into
an aluminum mold (40 × 5.7 × 0.9 mm), which was fixed between
glass plates. Resins containing DETA or IPDA were cured at 40 and 80
°C, respectively for 24 h followed by a postcure at 120 and 150 °C,
respectively for 24 h.
Thermal Analysis and Flexural Testing. Glass transition
temperature was determined by differential scanning calorimetry on
a Q1000 instrument (TA Instruments, U.S.A.) by subjecting cured
epoxy resins to a heat−cool−heat cycle from 0 to 200 °C at 10 °C/
min under a nitrogen atmosphere. Cure behavior was determined
using the same instrument by heating freshly prepared resins from 30
to 200 °C at 5 °C/min under a nitrogen atmosphere. Cured epoxy
resins were analyzed on a Q500 thermogravimetric analyzer (TA
Instruments, U.S.A.) to determine mass loss as a function of
temperature by heating to 500 °C at 10 °C/min under a nitrogen
atmosphere. The statistic heat-resistant index temperature (Ts) was
calculated using T5% and T30% (temperature at 5% and 30% weight
loss) according to the following equation:
Ts = 0.49[T5% + 0.6(T30% − T5%)] (1)
Cured epoxy resins were conditioned at 23 °C and 50% relative
humidity for at least 24 h. Three-point bending was performed using
an RSA-G2 dynamic mechanical thermal analyzer (TA Instruments,
U.S.A.). The support span length was 15 mm (span to thickness ratio:
16−17). The specimens were tested to failure, where possible. Average
values and 95% confidence intervals were determined from at least
four replicates, except for LHOEP/BADGE 1:9 and the IPDA-cured
specimens that were tested in duplicate due to limited amounts of
sample.
■
RESULTS AND DISCUSSION
Hydrogenolysis. Native lignin in Pinus radiata wood was
depolymerized by mild hydrogenolysis to a complex mixture of
DOI: 10.1021/acs.biomac.7b00767
Biomacromolecules 2017, 18, 2640−2648
Biomacromolecules
Figure 1. Approach used to prepare cured epoxy resins from lignin hydrogenolysis products.
aromatic polyols composed of monomers, dimers, and
oligomers, as described previously.42 In this study, scaling-up
the reaction 6-fold in a 450 mL reactor gave the lignin
hydrogenolysis oil product (LH) in a yield of 78% w/w on
starting lignin. Consistent with previous findings, the main
monomers in the oil product were dihydroconiferyl alcohol
(DCA, 4-(3-hydroxypropyl)-2-methoxyphenol) and 4-propyl
guaiacol (PG, 4-propyl-2-methoxyphenol) constituting approx-
imately 22% and 3% w/w, respectively (Figure 1).42 Various
dimers and oligomers of DCA and PG represented
approximately 75% of the oil product. The oligomers ranged
in degree of polymerization from 3 to 7, as determined by gel
permeation chromatography (Figure 2). LH was fractionated
Figure 2. Molecular weight profiles of lignin hydrogenolysis products
and their epoxy derivatives.
by solubility in diethyl ether. The diethyl ether-insoluble
fraction (LHO), which was enriched in oligomers (Figure 2B),
made up 50% w/w of LH and was used along with LH to
prepare epoxy resins. The weight-average molecular weight
(Mw) for LH and LHO was 667 and 898 g/mol, respectively.
Both LH and LHO had a polydispersity index (PDI) of 1.5.
Quantitative 31P NMR spectroscopy is an important
analytical technique for quantifying the different types of
hydroxyl groups in lignin (Figure 3).43,49 A high number of
phenolic hydroxyl groups is generally advantageous as they can
be reacted with epichlorohydrin to generate epoxide function-
ality, that is, glycidyl ethers (Figure 1). The LH and LHO
products contained 4.1 and 4.4 mmol/g of total phenolic
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Figure 3. Quantitative 31P NMR spectrum of lignin hydrogenolysis oil
after reaction with the phosphitylating agent.
hydroxyl groups, respectively (Table 1). This compares with 1.1
mmol/g for enzymatic mild acidolysis lignin isolated from P.
radiata wood42 and 2.3 mmol/g for a depolymerized lignin that
was used to produce epoxy resins.50 The hydrogenolysis
reaction cleaves β-O-4 ether linkages in the native wood lignin
to liberate new phenolic hydroxyl groups. 31P NMR spectros-
copy also gives information on the chemical environment of the
phenolic hydroxyl groups, namely, whether these groups
present in C9 phenylpropanoid units are (i) bonded to H at
the 5-position (uncondensed) or (ii) bonded to another C9
unit at the 5-position (condensed), such as β-5, 5-5, or 4-O-5
linked units (Figures 3 and 4, Table 1).43 The phenolic
hydroxyl groups in the monomers, DCA and PG (Figure 1),
analyze as uncondensed hydroxyl groups, whereas the dimers
and oligomers of DCA and PG could contain both
uncondensed and condensed phenolic hydroxyl groups.
DOI: 10.1021/acs.biomac.7b00767
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Biomacromolecules Article

Table 1. Hydroxyl Group Content of the Lignin Hydrogenolysis Products and Their Epoxy Derivatives by Quantitative 31P
NMR Spectroscopy
phenolic OH (mmol/g)
sample β-5 4-O-5 5-5 uncondensed guaiacyl (G) p-hydroxy phenyl total acidic OH (mmol/g)
LH 0.53 (0.008)a 0.20 (0.003) 0.76 (0.012) 2.56 (0.019) 0.06 (0.007) 4.11 (0.06) 0.14 (0.005)
LHEP 0.07 0.01 0.02 0.03 0.001 0.13 0.003
% reacted 87 95 98 99 99 97 98
LHO 0.81 0.34 1.17 1.95 0.10 4.36 0.16
LHOEP 0.16 0.02 0.05 0.13 NDb 0.37 0.003
% reacted 80 93 96 93 100 92 98
a
Standard deviations in parentheses for LH analyzed in triplicate. bNot detected.

Figure 4. Examples of condensed and uncondensed structures in

lignin hydrogenolysis products.

Consequently, the oligomeric fraction of the hydrogenolysis oil

(LHO) contained a greater proportion of condensed phenolics
(Table 1) compared to the whole oil (LH). In this study,
molecules with at least two phenolic hydroxyl groups (i.e.,
dimers and oligomers) were required to make cross-linking
epoxy resins.
Glycidylation Reaction. The main product from the
reaction of LH with epichlorohydrin was confirmed as the
expected glycidyl ether by 1H, 13C and 2D HSQC NMR
spectroscopy. Signals in the HSQC spectrum of the lignin
hydrogenolysis epoxy prepolymer (LHEP), labeled as 1, 2, and
3, are characteristic of a glycidyl ether group connected to a
lignin guaiacyl unit (Figure 5). The 1H and 13C chemical shifts
of the glycidyl signals were consistent with those reported in
the literature.28
Quantitative 31P NMR spectroscopy of LHEP and the
oligomeric epoxy prepolymer (LHOEP) showed that 97% and
92% of the phenolic hydroxyl groups were derivatized,
respectively (Table 1). The condensed β-5 phenolic hydroxyl
group was less reactive compared to the uncondensed phenolic
hydroxyl group (Table 1). This could be due to steric
hindrance of the reaction. Similarly, Fache and co-workers
(2016) found that the phenolic hydroxyl groups in syringyl-
based (S-type) model compounds, with a methoxy group at the
5-position, gave lower conversions on glycidylation compared
to guaiacyl-based (G-type) lignin models.27 Interestingly, the
other condensed phenolic hydroxyl groups (e.g., 5-5 and 4-O-5
linked) were not affected to the same degree as the phenolic
hydroxyl groups in β-5 structures (Table 1), suggesting factors
other than steric hindrance influence the reactivity.
2643
Figure 5. Partial HSQC NMR spectrum of LHEP showing glycidyl
ether functionality.
Both LHEP and LHOEP had higher molecular weights than
the lignin hydrogenolysis starting materials, LH and LHO
(Figure 2). Potential oligomerization reactions between newly
formed glycidyl groups and unreacted phenolic hydroxyl
groups, which would lead to higher molecular weight resins,
were minimized by using an excess of epichlorohydrin in the
reaction. Indeed, the Mw for LHEP and LHOEP increased by
only 60−70% to 1084 and 1514 g/mol (Table 2), respectively,
compared to the starting materials. When compared against
commercial BADGE resins, the average molecular weight of
LHEP was intermediate between typical liquid and solid
BADGE resins. The molecular weight of LHOEP was
equivalent to a solid BADGE resin with a degree of
polymerization of 2.8 The PDI for the LHEP and LHOEP
products was 1.8 (Table 2), which was similar to that of low
molecular weight BADGE resins.51 Higher PDI values have
been reported for epoxy resins produced from depolymerized
Kraft (PDI 3.5), organosolv (PDI 2.8), and hydrolysis (PDI
4.6) lignins.39,50 Polydispersity is a measure of the molecular
weight distribution. In this study, a low PDI was desirable as it
gave a more molecularly homogeneous prepolymer which was
reflected in the ability to process the resin.
An important criterion for epoxy resins is the epoxide
content, which is commonly referred to as the epoxy equivalent
weight (EEW), expressed as the weight of resin to obtain one
DOI: 10.1021/acs.biomac.7b00767
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Biomacromolecules
Table 2. Chemical Properties of the Epoxy Prepolymers
resin Mn (g/mol) Mw (g/mol) PDI EEW (g/eq)
b
LHEP 610 1084 1.8 359 (17)
LHOEP 837 1514 1.8 452 (1)
a
As 40% solutions in diethylene glycol monobutyl ether. bStandard deviations are given in parentheses.
equivalent epoxide group.8 The lower the EEW the greater the
potential cross-linking density in the cured epoxy resin. The
EEW values for LHEP and LHOEP were 359 and 452 g/eq,
respectively (Table 2). This translates to approximately one
epoxide group per 1.5 lignin C9 units in the LHEP resin and
one epoxide group per 1.9 lignin C9 units in the LHOEP resin,
for an estimated molecular weight of a glycidylated C9 lignin
unit of 238 g/mol. The theoretical EEW values expected for
LHEP and LHOEP were 300 and 307 g/eq, respectively, based
on the quantitative 31P NMR results (Table 1). The difference
between the actual and theoretical values was possibly due to
side reactions that can occur during the glycidylation reaction.8
Commercial BADGE resins can have a wide range of EEW
values, from 174 up to 6000 g/eq.8 BADGE used in this study
had an EEW of 174 g/eq. The EEW values for LHEP and
LHOEP were lower than reported for epoxy resins made from
depolymerized softwood Kraft lignin (768 g/eq) and hardwood
organosolv lignin (537 g/eq),39 indicating more cross-linking is
possible with lignin hydrogenolysis products from native
softwood lignin.
Chlorine content is an important quality indicator for epoxy
resins.8 High chlorine values can result in corrosivity issues in
cured resins, therefore low values are desirable. The total
chlorine content of LHEP and LHOEP was 1.0% and 1.7%,
respectively (Table 2). The hydrolyzable chlorine content of
LHEP and LHOEP was 0.1% and 0.3%, respectively (Table 2).
Hydrolyzable chlorine content provides a measure of the
presence of chlorohydrin intermediates (Figure 6) from
Figure 6. Main glycidylation reaction pathway of lignin hydrogenolysis
products showing chlorohydrin intermediate.
incomplete dehydrohalogenation that can reduce the potential
for the resin to cross-link with curing agents. Chlorine content
is rarely reported in publications on biobased epoxy resins.
Zhao and Abu-Omar (2015) reported a hydrolyzable chlorine
content of 0.5% and a total chlorine content of 3.4% for an
epoxy functionalized lignin model compound.34 A low level of
hydrolyzable chlorine was achieved in this study by applying a
postreaction alkali treatment.52 For glycidylation reactions,
optimized conditions are needed to achieve low levels of total
chlorine. This is difficult to achieve at a small scale. Undesirable
side reactions can lead to bound chlorides which are not readily
saponified with NaOH solutions.8 In commercial resins, typical
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hydrolyzable chlorine (%) total chlorine (%) viscositya (cP)
0.1 (0.04) 1.0 (0.03) 55
0.3 (0.04) 1.7 (0.02) 132
hydrolyzable and total chlorine contents range from 0.02−0.1%
and 0.1−0.2%, respectively.8
Cured Epoxy Resins Containing BADGE. Blending and
Curing. The viscosities of LHEP and LHOEP as 40% solutions
in diethylene glycol butyl ether were 55 and 132 cP,
respectively (Table 2). These viscosities were higher than for
a typical liquid BADGE resin, but lower than for a solid
BADGE resin with a degree of polymerization of 2.8 Adding 9%
of a reactive diluent was helpful in reducing the viscosity of the
epoxy resins so that they could be mixed with the curing agent
and remain workable at 40 °C. Reactive diluents are typically
used to reduce the viscosity of epoxy resins without severely
impacting on their overall properties53 and are used at levels up
to 20% w/w.8 Using this system gave workable resins, whereas
other researchers have incorporated solvents or used elevated
temperatures (70−130 °C) in order to effectively process
lignin-based epoxy resins.24,27,28,33,39
We first investigated DETA for curing the lignin-based epoxy
prepolymers as it is used commercially as an aliphatic curing
agent for curing epoxy resins at ambient temperature.8 Cured
epoxy resins produced from LHEP and DETA resulted in
specimens that were brittle and easily broken when removed
from the mold. The brittleness was attributed to the oligomer
molecules in the resin that contained multiple glycidyl ether
groups. These are analogous to multifunctional epoxy novolac
resins based on phenol formaldehyde novolacs that have high
cross-linking densities, which can result in increased brittle-
ness.8 It is common for commercial epoxy resins to be
formulated with multiple components to give optimum
processability and performance.8 Therefore, we investigated
the potential to formulate LHEP and LHOEP with BADGE.
DETA-cured epoxy resin specimens suitable for mechanical
testing could be prepared by blending LHEP with BADGE in
mass ratios of up to 3:1 and blending LHOEP with BADGE in
ratios of up to 1:3 (Figure 7). Preparation of specimens for
Figure 7. Cured epoxy resin specimens.
property testing using higher proportions of LHEP and
LHOEP was difficult due to processing limitations, except for
a thermal analysis specimen of the 100% LHEP epoxy resin.
Hence, LHEP was tested as a partial replacement for BADGE,
while LHOEP was tested as a potential performance enhancing
additive.
The cured epoxy resins were all transparent, although those
containing LHEP and LHOEP were amber in color (Figure 7).
The color is unlikely to be a major limitation for most epoxy
resin applications.
DOI: 10.1021/acs.biomac.7b00767
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Thermal Properties. The glass transition temperature (Tg)
values of the DETA-cured epoxy resins produced from LHEP/
BADGE blends were lower than that of the BADGE control
resin, with a range of 68−80 °C (Table 3). Higher proportions
Table 3. Thermal Analysis Data for Epoxy Resin Blends
Containing BADGE and Cured with DETA
resin Tg (°C) T5% (°C) Ts (°C)
a
BADGE 117 (0.7) 328 (0.8) 169 (0.2)
LHEP/BADGE 1:1 80 289 161
LHEP/BADGE 2:1 70 270 156
LHEP/BADGE 3:1 68 258 151
LHEP 53 236 144
LHOEP/BADGE 1:9 111 325 169
LHOEP/BADGE 1:3 104 311 165
a
95% confidence intervals are given in parentheses for the BADGE
resin based on four replicates.
of LHEP resulted in a lower Tg, which was consistent with the
100% LHEP resin having the lowest Tg of 53 °C. This trend
was the same for the cured LHOEP/BADGE resins, although
the differences relative to the BADGE resin were less
pronounced due to the lower proportions of LHOEP used in
the blends. The Tg of the cured BADGE resin was similar to
that reported previously (117 vs 119 °C).54 The lower Tg of the
cured blends could be due to several factors. BADGE is a rigid
molecule with the aromatic rings joined by a isopropylidene
bridge (Figure 1), whereas LHEP and LHOEP contain dimers
and oligomers with both rigid (e.g., 5-5) and flexible (e.g., β-5)
linkages (Figure 4). The flexible structures are likely to reduce
the Tg. Methoxy groups that are associated with the lignin
structures are known to reduce the Tg of cured epoxy resins.30
By combining a depolymerized lignin with an annulation
reaction prior to glycidylation, Kaiho and co-workers (2016)
were able to produce epoxy resins with Tg values as high as 134
°C.55
The cured LHEP/BADGE and LHOEP/BADGE resins were
less thermally stable than the BADGE resin (Table 3). The
initial decomposition temperature (T5%) was lowest for
specimens containing the highest proportion of LHEP and
LHOEP, and was consistent with the 100% LHEP resin having
the lowest T5% of 236 °C. The statistic heat-resistant index
temperature (Ts) is characteristic of the thermal stability of the
cured resins.35 The Ts values had the same trend as for the T5%
values (Table 3). The reduction in thermal stability is likely due
to the presence of methoxy groups on the aromatic ring, as they
are known to decrease thermal stability by means of electron
donation to the aromatic ring.56 The thermal results suggest
that cured epoxy resins containing LHEP and LHOEP may be
less suitable than BADGE-based resins in high temperature
applications.
The onset curing temperature (To) and the peak curing
temperature (Tp) for the BADGE resin was 67 and 91 °C,
respectively. The LHEP/BADGE 1:1 and 2:1 blends had a
reduced To of 46 and 43 °C and a reduced Tp of 80 and 78 °C,
respectively. This curing behavior is attributed to the presence
of primary aliphatic hydroxyl groups associated with the DCA
moieties (Figure 1) in LHEP. Hydroxyl groups are known to
accelerate the rate of cure of epoxy resins with amine curing
agents,8 and have been implicated in promoting the curing
reaction of epoxy resins produced from lignin model
compounds and other depolymerized lignins.34,39
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Mechanical Properties. The measured mechanical proper-
ties of the LHEP/BADGE and LHOEP/BADGE blends cured
with DETA were superior to the BADGE control resin (Figure
8). The cured LHEP/BADGE 2:1 blend resulted in flexural
Figure 8. Flexural properties of epoxy resin blends containing BADGE
and cured with DETA (error bars are 95% confidence intervals of at
least four replicates).
modulus and strength values that were 52% and 28% greater,
respectively, than BADGE alone. Increasing the proportion of
LHEP in the blend from 67% to 75% resulted in a decline in
both the flexural modulus and, to a greater degree, the flexural
strength. The flexural strength values of replicate specimens of
the cured LHEP/BADGE 3:1 blend were highly varied
(ranging from 80 to 159 MPa), which was attributed to
increased brittle behavior. The results indicated there was no
advantage in testing cured LHEP/BADGE blends at ratios
lower than 1:1 (Figure 8). The cured LHOEP/BADGE 1:3
blend resulted in a flexural modulus and strength that was 26%
and 38% greater, respectively, than BADGE alone. The increase
in the flexural modulus was greater than for the LHEP/BADGE
1:1 blend and the flexural strength was the highest of all the
specimens measured at 163 MPa. An increase in the flexural
strength was observed even when the proportion of LHOEP to
BADGE was only 10% compared to the BADGE resin (140 vs
118 MPa).
These results imply that the lignin-derived oligomers play a
key role in improving the flexural modulus and strength of the
cured epoxy resin blends. For the LHEP/BADGE blends,
monomers in the lignin hydrogenolysis oil with single glycidyl
groups potentially act more as reactive diluents, contributing
little to the mechanical properties of the cured resins. In this
regard, choice of the lignin feedstock for hydrogenolysis is
important, as softwood native lignins give higher yields of
oligomeric products compared to hardwood lignins.40,42 Lignin
monomers can be used to make a cross-linked epoxy polymer
if, for example, they contain at least two phenolic hydroxyl
groups that can be glycidylated.34 The presence of methoxy
groups in the lignin hydrogenolysis products is likely to
contribute to the superior mechanical properties of the cured
LHEP/BADGE and LHOEP/BADGE blends. Hernandez and
co-workers (2016) found that methoxy groups improved the
modulus of cured epoxy resins derived from vanillyl alcohol,30
and hydrogen bonding between methoxy groups and hydroxyl
DOI: 10.1021/acs.biomac.7b00767
Biomacromolecules 2017, 18, 2640−2648
Biomacromolecules Article

Table 4. Effect of Curing Agent (DETA, IPDA) on Thermal and Mechanical Properties of BADGE and Blended Cured Resins
DETA IPDA
resin Tg (°C) flexural modulus (GPa) flexural strength (MPa) Tg (°C) flexural modulus (GPa) flexural strength (MPa)
a
BADGE 117 (0.7) 3.1 (0.03) 118 (1) 162 (0.2) 2.9 (0.2) 146 (6)
LHEP/BADGE 1:1 80 3.7 129 100 3.8 141
LHOEP/BADGE 1:3 104 3.9 163 135 3.1 155
a
95% confidence intervals are given in parentheses for the BADGE resin based on at least three replicates.

groups formed during curing has been implicated in improving
mechanical strength.4 Nonetheless, other factors, such as
monomer to oligomer ratio and cross-linking densities, can
also influence mechanical properties.
Other researchers have prepared cured epoxy resins based on
monomers that can be derived from lignin, such as vanillin,27,28
vanillyl alcohol,30 isoeugenol,32 and propyl guaiacol,34,36
however, no comparable information is provided on mechanical
properties. In related work, Ferdosian and co-workers (2016)
measured mechanical properties of glass fiber-reinforced
plastics prepared using BADGE blended with epoxy resins
made from depolymerized softwood Kraft and hardwood
organosolv lignins.39 They also observed improvements in
flexural modulus and strength, but mainly at a low blend ratio
of 1:3 lignin-based epoxy to BADGE. In our work, we were able
to increase both the flexural modulus and strength in higher
blend ratios up to 2:1 lignin-based epoxy to BADGE.
Alternative Curing Agent. Selected epoxy resin blends were
cured with IPDA, a cycloaliphatic curing agent commonly used
in industry, to investigate the effect of a different curing agent.
These cured epoxy resins had higher Tg values compared with
those cured with DETA (Table 4). Cycloaliphatic curing agents
are known to enhance the thermal properties of cured resins
compared to aliphatic amine curing agents.8 As with DETA,
blending LHEP and LHOEP with BADGE resulted in cured
epoxy resins with lower Tg values relative to the BADGE
control resin. The flexural modulus of the LHEP/BADGE 1:1
blend resin was similar when cured with either curing agent
(Table 4). This was also true for the BADGE control resin. The
LHEP/BADGE 1:1 blend that was cured with IPDA no longer
had a flexural strength performance advantage over the BADGE
resin, compared to curing with DETA. Curing BADGE with
IPDA has previously been reported to increase flexural strength
compared to curing with DETA.54 The flexural properties of
the IPDA-cured LHOEP blend were similar to the IPDA-cured
BADGE resin and reduced compared to the DETA-cured
LHOEP blend (Table 4). Overall, these results indicated that
blending LHEP and LHOEP with BADGE, and curing with
IPDA, gave mechanical properties that were similar to the
BADGE control resin.
Cured Epoxy Resins Containing Glycerol Diglycidyl
Ether. LHEP was blended with GDGE to produce epoxy resins
containing entirely biobased components. GDGE has been
used as an epoxy prepolymer in lignin-containing epoxy
resins.22,57 The addition of the reactive diluent was not
required for the LHEP/GDGE blends as the viscosity was
sufficiently low to cast specimens at 40 °C (e.g., Figure 7). The
Tg values of the blends that were cured with DETA were similar
to the GDGE control resin (Table 5) and approximately 60 °C
lower than the BADGE control resin. The cured GDGE resin
had reduced thermal stability compared to the BADGE resin
and addition of LHEP decreased this further (Table 5), as was
seen with the LHEP/BADGE blends. These results suggest that
2646
Table 5. Thermal and Mechanical Properties of Epoxy Resin
Blends Containing GDGE and Cured with DETA
Tg T5% Ts flexural modulus flexural strength
resin (°C) (°C) (°C) (GPa) (MPa)
GDGE 58 260 139 2.8 (0.6)a 95 (8)
LHEP/ 59 242 139 3.7 (0.1) 121 (2)
GDGE 1:1
LHEP/ 60 220 136 4.0 (0.2) 140 (7)
GDGE 2:1
a
95% confidence intervals are given in parentheses.
LHEP/GDGE epoxy resin blends would be restricted to lower
temperature applications.
The flexural modulus and strength of the cured epoxy resins
were improved with increasing proportions of LHEP in the
LHEP/GDGE blends (Table 5). The cured LHEP/GDGE 2:1
blend resulted in flexural modulus and strength values that were
43% and 47% greater, respectively, than the GDGE control
resin, and were intermediate between the modulus and strength
values obtained for the cured LHEP/BADGE 1:1 and 2:1
blends. The LHEP/GDGE 2:1 blend produced a cured resin
with a 29% greater flexural modulus and 19% greater flexural
strength than the BADGE control resin. This indicates that it is
possible to make 100% biobased epoxy resins that, when cured,
have superior mechanical properties compared to BADGE
resins.
Summary of Mechanical Performance. In summary, the
flexural properties were very promising, with the cured LHEP/
BADGE and LHOEP/BADGE blends performing better than
the industry standard BADGE resin. LHEP has potential as a
biobased partial replacement for BADGE. Alternatively, LHEP
used in combination with GDGE warrants further investigation
as a complete replacement for BADGE. LHOEP appears to
have potential as a biobased performance enhancing additive
for BADGE-based resins. More extensive formulation and
property testing is needed to fully assess the potential of these
lignin hydrogenolysis products in developing novel biobased
epoxy resins.
■ CONCLUSIONS
Mild hydrogenolysis of native softwood lignin produces a
polyol product that can be used to prepare novel biobased
epoxy resins. Reacting this lignin-based polyol with epichlor-
ohydrin gave an epoxy prepolymer that, when blended with
BADGE or GDGE, resulted in cured epoxy resins with a greater
flexural modulus and strength to those made from BADGE
alone. This is the first reported example of a deconstructed
native softwood lignin being used to produce concept epoxy
resins with superior mechanical properties to the industry
standard. Further work is needed to improve and scale-up the
lignin hydrogenolysis process, and to optimize the glycidylation
and resin formulation chemistry. The promising performance of
these concept epoxy resins suggests that with this further work,
DOI: 10.1021/acs.biomac.7b00767
Biomacromolecules 2017, 18, 2640−2648
Biomacromolecules
a viable and fully biobased epoxy resin with properties
comparable to the bisphenol A-derived industry standard may
be realized.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: daniel.vandepas@scionresearch.com. Phone: +64-7-
343-5899. Fax: +64-7-348-0952.
ORCID
Daniel J. van de Pas: 0000-0002-6415-9569
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This research was supported by the New Zealand Ministry of
Business Innovation and Employment via Scion Core funding.
The authors wish to acknowledge Ibrar Hussain for technical
assistance with lignin hydrogenolysis.
■
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2648 DOI: 10.1021/acs.biomac.7b00767

Biomacromolecules 2017, 18, 2640−2648