Research Article

pubs.acs.org/journal/ascecg

Ultrastiff Biobased Epoxy Resin with High Tg and Low Permittivity:

From Synthesis to Properties
Jintao Wan,† Jianqing Zhao,‡ Bin Gan,† Cheng Li,§ Jon Molina-Aldareguia,† Ying Zhao,‡ Ye-Tang Pan,†
and De-Yi Wang*,†
†
IMDEA Materials Institute, C/Eric Kandel, 2, Getafe, Madrid 28906, Spain
‡
School of Materials Science and Engineering, South China University of Technology, 510640 Guangzhou, China
§
State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University, Zheda Road
38, Hangzhou 310027, China
*
S Supporting Information

ABSTRACT: Harvesting biobased epoxy resins with im-

proved thermomechanical properties (e.g., glass transition
temperature Tg and storage modulus), mechanical and
dielectric similar and even superior to that of bisphenol A
epoxy resin (DGEBA) is vital to many applications, yet
remains a substantial challenge. Here we develop a novel
eugenol-based epoxy monomer (TEU-EP) with a branched
topology and a very rich biobased retention (80 wt %). TEU-
EP can be well cured by 3,3′-diaminodiphenyl sulfone
(33DDS) and the resultant TEU-EP/33DDS system can be
considered as a “single” epoxy component, exhibiting adequate
reactivity at high processing temperatures. Importantly,
compared with DGEBA/33DDS, TEU-EP/33DDS achieves
a 33 °C, 39% and 55% increment in the glass transition temperature, Young’s modulus, and hardness, respectively, and shows the
improved creep resistance and dimensional stability. TEU-EP/33DDS is also characterized by the considerably reduced
permittivity, dielectric loss factor, and flammability with high yield of pyrolytic residual. Overall, TEU-EP endows the cured
epoxy with a number of the distinguished properties outperforming its DGEBA counterpart, and therefore may find practical
applications in demanding and even cutting-edge areas.
KEYWORDS: Biobased epoxy monomer, Synthesis, Curing, Mechanical and thermal properties, Dielectric properties

■ INTRODUCTION
With accelerating consumption of fossil-based unrenewable
resources, transformation of renewable feedstocks, especially
biomasses, to sustainable fuel and polymeric materials becomes
increasingly important. Thermosetting polymeric materials are
generally unable to rework or reshape after use, which will not
only hasten the consumption of unrenewable resources but also
cause the accumulative disposition of thermosetting wastes in the
environment. Among the thermosetting polymers, epoxy resins
find a myriad of applications as in coatings, adhesives,
composites, construction, electrical engineering, and electronics
owing to their attractive comprehensive properties and wide
applicability.1,2 Today approximately 90% of epoxy resins,
DGEBAs, are produced from petroleum-based bisphenol A
and epichlorohydrin worldwide.3 Bisphenol A is synthesized
from unrenewable petroleum-based phenol and acetone, and
epichlorohydrin is mainly synthesized from oxidation of allyl
chloride though a considerable portion comes from renewable
glycerol. Also, epichlorohydrin is carcinogenic, and bisphenol A
can cause estrogen-like long-lasting effects on living organisms.
As a result, the presence of bisphenol A in food packaging
materials has been banned in EU, USA, and Canada, and as a
result polyprolene is now widely used to fabricate the milk bottle
to replace bisphenol A-type polycarbonate (PC).
Epoxy resins derived from the renewable biomasses3,4 become
the most promising alternative for petroleum-based counter-
parts. Among them, epoxidized soybean oils5,6 are massively
produced and used, but in practical applications they cannot
serve as an epoxy matrix alone, because of their inferior
properties (e.g., low glass temperature, modulus and thermal
properties) compared with standard DGEBAs, arising from their
long and highly flexible aliphatic skeleton. Instead, they are
usually applied as plasticizers or processing agents for synthetic
resins, especially, polyvinyl chloride (PVC). To improve the
properties of biobased epoxy resins, rosin,7−9 gallic acid,10−12
vanillic acid,11 vanillin,13,14 itaconic acid,15 dimer fatty acid,16
sucrose fatty acid esters,17 isosorbide,18−20 cinnamic acid and
dipentene,21 cardanol,22,23 sugar,24 furan alcohol,25 and others26
Received: March 7, 2016
Revised: April 6, 2016
Published: April 21, 2016

© 2016 American Chemical Society 2869 DOI: 10.1021/acssuschemeng.6b00479

ACS Sustainable Chem. Eng. 2016, 4, 2869−2880
ACS Sustainable Chemistry & Engineering
Scheme 1. Molecular Structures of DGEBA, Synthesized Eugenol-Based Epoxy Resin (TEU-EP), and Curing Agent (33DDS)a
a
Theoretically, DGEBA and TEU-EP have the epoxy functionalities of two and three, respectively, and 33DDS has the amino hydrogen
functionalities of four.
have been used to synthesize biobased epoxy monomers.
Moreover, recent advances in biobased epoxy foams27 and
biobased biodegradable28,29 and flame retardant30,31 epoxy resins
as well as biobased epoxy curing agents32−36 further expand the
scope of biobased epoxy chemistry and technology, which will
greatly extend potential applications of biobased epoxy systems.
More interestingly, eugenol, 4-allyl-2-methoxyphenol, ex-
tracted from plants (e.g., clove oil), is one kind of essential oils
with relatively low cost, consisting of the rigid aromatic ring
substituted by an allyl group, a hydroxyl group, and a methoxyl
group.37−39 Eugenol-based thermosets have been attracting
increasing research interests. Harvey et al.37 reported the eugenol
based cyanate ester that could be well cured at a high temperate,
and the cured epoxy exhibited excellent thermal stability up to
350 °C with a Tg of 186 °C. Neda et al.38 reported an eugenol-
based bismaleimide with high Tg (350 °C) and modulus (2.6−
3.1 GPa). Eugenol-based benzoxazines40−42 and eugenol-based
unsaturated resins43 were reported with improved specific
properties.
It seems more interesting to develop eugenol-based epoxy
resins for their easy processing, highly tailorable and versatile
properties, and thus wide potential applications. Zhang et al.44
reported an eugenol-based epoxy resin (Eu-Ep) with biobased
content of 62.7 wt % via epoxidation of eugenol’s double bond,
followed by O-glycidylation of its hydroxyl group. An acid
anhydride-cured Eu-Ep showed a glass temperature of 114 °C.
On the other hand, according to our very recently developed
strategy,45,46 two eugenol moieties were bridged by the aliphatic
ether or aromatic ester bonds, to yield to bifunctional eugenol-
based epoxy resins, DEU-EP and TPEU-EP. They had the
increased net biobased content as high as 70.2 wt %, and the
cured epoxy showed the increased moduli and reduced
flammability. In particular, 3,3′-diaminodiphenyl sulfone
(33DDS) cured TPEU-EP was self-extinguishing in a vertical
burning test,46 expressing rather low flammability. However, the
melting temperature of TPEU-EP was rather high (>150 °C),
and the glass temperature of the cured epoxy product was still
lower than that of DGEBA system.
Up to now, an open issue in the field of biobased epoxy resins
is to simultaneously enhance thermal resistance (especially glass
transition temperature), mechanical properties, and flame
retardancy of biobased (including eugenol-based) epoxy resins
outperforming DGEBAs in as many properties as possible.
Additionally, the retained biobased contents of the resulting
epoxy monomers still need further improving to more efficiently
use biobased precursors. Moreover, biobased epoxy resins with
improved dielectric properties are still not yet achieved, though
epoxy-based materials with good dielectric properties are widely
used in the microelectronic industry. To meet these challenges,
here we develop an updated, facile strategy to realize a novel
trifunctional eugenol-based epoxy monomer, TEU-EP (Scheme
1), by reacting eugenol with cyanuric chloride in a high-efficient
2870
Research Article
phase-transfer catalytic system, followed by epoxidation of the
inherited allyl double bonds. In the TEU-EP molecule, a low-
molecular-weight triazine concentrator links three eugenol
moieties together, which leads to the further increased biobased
retention as high as 80 wt %. Also thanks to this triazine
concentrator, TEU-EP has derived a branched molecular
topology, which causes the increased epoxy functionalities but
decreased melting temperature compared with our reported
eugenol-based epoxy resins.45,46 Moreover, this highly rigid and
low polarizable triazine moiety is expected to greatly contribute
to mechanical, thermal and electrical properties of the resulting
epoxy system. Here in the presence of 3,3′-diaminodiphenylsul-
fone (33DDS) as the curing agent, the influence of TEU-EP’s
molecular structure on the curing behaviors, thermomechanical
and mechanical properties, dielectric characteristics, thermal
decomposition, and flammability are systematically investigated,
by comparing with a standard DGEBA/33DDS system. It will be
showed that cured TEU-EP/33DDS is highlighted by the
ultrahigh Tg, Young’s modulus and hardness, outstanding
thermomechanical properties, low permittivity and dielectric
loss, and reduced flammability.
■ EXPERIMENTAL SECTION
Materials. Eugenol, cyanuric chloride, benzyltriethylammonium
chloride, chloroperoxybenzoic acid (mCPBA, ∼ 77%), sodium
hydroxide, chloroform, dichloromethane, acetone, menthol, sodium
hydroxide, and tetraethylammonium bromide were purchased from
Sigma-Aldrich. 3,3′-Diaminodiphenylsulfone (33DDS, > 98%) was
brought from TCI Europe. Bisphenol A epoxy resin (DGEBA) under
trademark of Epoxy Resin C (epoxy value = 0.531 mol epoxide/100 g)
was obtained from Faserverbundwerkstoffe Composite Technology,
Germany. Other materials were used as received. The eugenol-based
epoxy resin (TEU-EP) was originally synthesized in our lab, whose
epoxy value was titrated to be 0.451 mol epoxide/100 g according to
ASTM D1652 (titrant HClO4 in acetic acid; reagent tetraethylammo-
nium bromide; indicator crystal violet; solvent CH2Cl2). The molecular
structures of DGEBA, TEU-EP, and 33DDS are shown in Scheme 1.
Molecular Structure Characterization. The FTIR spectra (KBr
pellet) of the synthesized epoxy resin and intermediate were registered
on a Nicolet iS50 spectrometer over the wavenumber range of 400−
4000 cm−1. The room-temperature 1H NMR (400.1 MHz) and 13C
NMR (101 MHz) spectra were recorded on a Varian Mercury AS400
spectrometer (5 mm Varian 4NUC probe). The solvent and internal
standard were CDCl3 and tetramethylsilane (TMS), respectively. The
mass spectrum of TEU-EP was recorded on a mass spectrometer
(Model LCD Deca xp max, Thermo Electron Corporation, USA) with
an ESI source. The sample was dissolved in chloroform and then diluted
with methanol before measurement.
Curing Behavior Characterization. A differential scanning
calorimeter (Q200, TA Instruments, USA) was used to study the
epoxy curing reaction. For the simplicity, we fixed the ratio of TEU-EP
or DGEBA to 33DDS according to the stoichiometry (epoxy ring: N−H
= 1:1 by mole). The mixture was dissolved in acetone with stirring, and
then, the solvent was removed at 50 °C in vacuum. The as-prepared
reaction mixture (10 ± 2 mg) was enclosed in an aluminum crucible and
DOI: 10.1021/acssuschemeng.6b00479
ACS Sustainable Chem. Eng. 2016, 4, 2869−2880
ACS Sustainable Chemistry & Engineering
Scheme 2. Synthesis of the Triazine-Bridged Eugenol-Based Epoxy Resin (TEU-EP)a
a
Reaction conditions: (i) eugenol/NaOH/H2O + cyanuric chloride/benzyltriethylammonium chloride/CHCl3, from 10 °C to reflux, 8 h; (ii)
chloroperoxybenzoic acid/CH2Cl2, from 0 °C to room temperature, 5 days.
subjected to a programmed temperature run. Four heating scans (3, 4.5,
6.7, and 10 °C/min) were registered on each fresh sample (in nitrogen
flow of 50 mL/min) from 20 to 300 °C to yield the nonisothermal curing
curves.
Preparation of Cure Samples. DGEBA or TEU-EP and 33DDS
(epoxy: N−H = 1:1) without solvent were heated to 140 °C with stirring
to form homogeneous mixture. Immediately, the reaction mixture was
casted into a preheated mold at 180 °C for 5 h. The released specimens
were polished and dried in vacuum at 40 °C for further testing.
Thermomechanical Property Characterization. The polished
epoxy specimens (35 mm × 10 mm × 2 mm) were subjected to the
thermo-mechanical analysis using a dynamic mechanical analyzer (DMA
Q800, TA Instruments). The specimen was mounted on a single
cantilever clamp, the oscillation frequency was 1 Hz, and the
displacement was 20 μm. Testing temperature ranged from 30 to 270
°C (3 °C/min). The glass temperature (Tg) was taken as the
temperature for maximum loss factor tan δ. A static mechanical analyzer
(DIL 402C, Netzsch, Germany) was used to evaluate the dimensional
stability of the cured samples (dimension Φ 10 mm × 18 mm) from
room temperature to 250 °C (5 K/min, in nitrogen) with a statistic force
of 0.2 N.
Nanoindentation Measurement. Nanoindentation is an effective
method of probing the site-specific mechanical properties at a very fine
scale. Because of a very tiny plastic deformation imposed, a very small
sample is adequate for finishing testing to acquire mechanical results
comparable to a bulk sample.47 During measurement, load−displace-
ment profiles are recorded and then used to calculate Young’s (elastic)
modulus, hardness and creep displacement.48 Nanoindentation has
been successfully used to gauge mechanical properties of cured epoxy
resins.49−51 The specimens for instrumented indentation were metal-
lurgically prepared with a great caution to minimize the influence of
residual stresses and plastic deformation. With an extremely low load,
the samples were finished with a final polish using colloidal silica (0.05
μm). A Hysitron TI 950 nanoindenter equipped with a Berkovich
diamond indenter was well calibrated by fused silica before testing. The
peak indentation load was set as 1, 3, 6, 9, and 12 mN with the fixed
loading and unloading rates of 300 and 450 μN/s, respectively. The
dwell time at the maximum indentation load was 5 s. To avoid the
interference among the different indents, the intervals among any
neighboring indents were greater than 100 μm. At least 36 indents were
conducted on each sample. To evaluate the creep behavior, the peak
indentation load, loading rate, and unloading rates were fixed at 9 mN,
300 μN/s, and 450 μN/s, respectively, with the dwell time of 600 s.
Dielectric Property, Thermal Stability and Flammability
Analysis. A Concept40 broadband dielectric spectrometer (Novocon-
trol Technologies GmbH & Co. KG) was used to study dielectric
properties of the cured epoxy. The bandwidth was between 10 Hz and 2
GHz, and the temperature was 25.0 °C with AC volt [Vrms] = 1.00 V.
The collected data were processed with the WinDETA. A thermogravi-
metric analyzer (Q50, TA Instruments) was used to study the thermal
decomposition of the cured epoxy. About 10 mg of cured epoxy was
heated from 40 to 850 °C (10 °C/min) under nitrogen (20 mL/min). A
FAA Micro combustion calorimeter (MCC, Fire Testing Technology,
UK) was used to evaluate the flammability of the cured epoxy according
to ASTM D7309. About 5 mg of sample was heated (1 °C/s) to 700 °C
in nitrogen (80 cm3/min). A gas flow (20 cm3/min, nitrogen/oxygen =
2871
Research Article
80:20, v/v) was used to carry out volatile products to the combustion
furnace (900 °C) of MCC.
General Procedure of Synthesis. As illustrated in Scheme 2, the
eugenol-based epoxy resin (TEU-EP) was synthesized by reacting
cyanuric chloride with eugenol to yield an intermediate (TEU) bearing
three allyl bonds followed by an epoxidation procedure to yield the
targeting epoxy monomer (TEU-EP).
Synthesis of TEU. In a typical procedure, eugenol (120.0 g, 710
mmol) was dissolved into 250 mL NaOH (29.2 g, 730 mmol) to yield a
sodium phenolate aqueous solution, and the solution was added to the
solution of cyanuric chloride (40.0 g, 216 mmol) and benzyltriethy-
lammonium chloride (1.0 g) in chloroform (800 mL) dropwise at 10−
20 °C with stirring for 1 h. The mixture was heated to 25−30 °C for 3 h
and then to reflux for 4 h. Subsequently, 10 g NaOH in 100 mL water
was added with stirring for 30 min. The organic fraction was washed with
water several times and then evaporated to yield the crude yellow solid.
The solid was purified by digesting in the mixture of hot methanol and
acetone (v/v = 4:1, 400 mL) twice to remove any byproducts, reactants,
and catalyst, then washed with water, and finally dried at 100 °C in
vacuum for 3 h to yield white powder, viz. TEU (114.0 g, 92.6%). FTIR
(KBr): ν = 3070 (w; Ph-H and C−H), δas = 2966 (w; CH3), δas =
2937 (w; CH2), δs = 2838 (w; CH2), ν = 1638 (m, CH2), ν = 1607 and
1508 (s, benzene ring), ω = 995 (w, CH2), γ = 909 (m, CH2). 1H
NMR (400 MHz, CDCl3-d3, δ): 3.4 (d, 6H, CH2−CHCH2), 3.8 (s,
9H, OCH3), 5.1 (t, 6H, CHCH2), 5.9 (m, 3H, CHCH2), 6.8 (m,
6H, CH2CH−CH2−Ph (H)), 7.1 (3H, CH2CH−CH2−Ph (H)).
Synthesis of TEU-EP. In a typical synthesis, TEU (15.0 g) was
dissolved into CH2Cl2 (800 mL) with stirring at 0 °C, and then mCPBA
(60 g) added in batches. The mixture was warmed to room temperature
with stirring for 5 days. After filtrating off the white solid byproduct, the
liquid phase was washed with 100 mL of 10% NaOH with stirring for 4 h
and then with 10 g of Na2SO3 in 100 mL water with stirring overnight.
The organic phase was extracted with 2% NaOH solution several times
and then with water until pH 7. After evaporation of the solvent, the
remaining solid was digested in methanol to yield a white powder (TEU-
EP) in 70% yield. FTIR (KBr): ν = 3048 (w; Ph-H), δas = 2989 (w; CH3)
and δas = 2939 (w; CH2), δs = 2839 (w; CH2), ν = 1605 and 1510 (s,
benzene ring), δas = 2966 (w; CH3) and δs = 2937 (w; CH3), 932 (w,
characteristic absorption band of epoxy group), γ = 724 (w; Ph-H). 1H
NMR (400 MHz, CDCl3-d3, δ): 2.5 (3H, epoxy ring (tran) H), 2.8 (6H,
epoxy ring (cis) and CH2 H), 3.1 (3H, epoxy ring (other) H), 3.7 (s, 9H,
OCH3 H), 6.8 (6H, Ph H), 7.2 (3H, Ph H). 13C NMR (101 MHz,
CDCl3, δ), 38.8 (CH2), 47.1 and 52.6 (epoxy ring), 56.0 (OCH3), 113.6,
121.1, 121.1, 122.4, 136.5, 139.6, and 151.1 (Ph); 173.8 (triazine ring).
ESI-Mass: [M + H+] = 616.43, [M + Na+] = 638.33.
■
RESULTS AND DISCUSSION
Synthesis and Structural Characterization of TEU-EP. A
facile strategy to prepare a triazine-bridged eugenol-based epoxy
monomer was developed using cyanuric chloride to react with
the hydroxyl group of eugenol in a high efficient phase-transfer
catalytic reaction system to yield an intermediate bearing three
allyl groups (TEU) in an excellent yield (92.6%). In this system,
sodium eugenolate is in aqueous phase and cyanuric chloride is in
CHCl3 phase. In the presence of the phase-transfer catalyst the
DOI: 10.1021/acssuschemeng.6b00479
ACS Sustainable Chem. Eng. 2016, 4, 2869−2880
ACS Sustainable Chemistry & Engineering Research Article

Figure 1. NMR spectra (CDCl3) of synthesized epoxy monomer (TEU-EP). (a) 1H NMR spectra of intermediate (TEU) and synthesized epoxy
monomer (TEU-EP). Proton signals of ally group are at 3.4, 5.1, 5.9, and 6.8 ppm, and those of epoxypropyl group are at 2.5, 2.8, and 3.1 ppm. (b) 13C
NMR spectrum of TEU-EP. The 13C chemical shifts of the epoxy rings are at 47.1 and 52.6 ppm.

Figure 2. DSC thermal and kinetic analytical curves of the curing reactions. (a) Nonisothermal thermographs from room temperature to 300 °C (10 °C/
min). (b) Multiple heating-rate nonisothermal thermographs and fractional conversion against time of TEU-EP/33DDS. (c) Effective reaction
activation energy (Eα) of TEU-EP/33DDS and averaged curing temperature against fractional conversion, α. (d) Isothermal conversion−time
dependence of TEU-EP/33DDS predicted from eq 3.

sodium eugenolate is captured and then transferred into CHCl3 reactive cyanuric chloride was used in our synthesis, there was no
phase to react with cyanuric chloride efficiently. Although highly gaseous emission during the synthesis and the whole reaction
2872 DOI: 10.1021/acssuschemeng.6b00479
ACS Sustainable Chem. Eng. 2016, 4, 2869−2880
ACS Sustainable Chemistry & Engineering
process was stable. The product could be easily to be isolated,
and the solvent (CHCl3) could be readily recycled. In practice,
cyanuric chloride is a massively produced and used chemical with
low cost. Then, the allyl groups of TEU were epoxidized with
mCPBA in large excess to yield triazine-bridged eugenol-based
epoxy monomer (TEU-EP) under a mild reaction condition
(CH2Cl2/room temperature). Also, there is no need to isolate
TEU and TEU-EP using column chromatography, which will be
attractive for their potential scaling-up synthesis for industrial
applications. It is worth to point out that although in the current
research unrenewable, toxic and high-cost mCPBA was used to
epoxidize TEU, it would be possible to find out another green
and low cost method to finish this process, which needs further
studies in the future.
Structurally, for TEU-EP, the signals related to the allyl groups
disappear, whereas the new ones due to the epoxy ring emerge
(Figure 1a). Additionally, IR absorption for the allyl CC bond
at (1638 cm−1) disappears, whereas a new absorption band at
933 cm−1 owing to epoxy ring appears (Figure S1). The further
evidence from the 13C NMR spectrum (Figure 1b) of TEU-EP
shows that carbon resonances accord well with the predicted
molecular structure. Moreover, the ESI-Mass spectrum (Figure
S2) further confirms that TEU-EP has the expected molecular
weight of 615.6 (experimental results [M + H+] = 616.4 and [M
+ Na+] = 638.3). All these results show the successful
achievement of TEU-EP.
Cure Reaction, Mechanisms and Kinetic Prediction.
Figure 2a shows the nonisothermal analytical curves of the curing
reaction of TEU-EP/33DDS and DGEBA/33DDS (10 °C/
min), from which we cannot observe any melting processes
during the heating run, whereas pristine TEU-EP and 33DDS
have their respective melting temperature range (Figure S3).
This observation indicates that TEU-EP and 33DDS could form
a eutectoid in molecular homogeneity after removal of cosolvent
(acetone) at low temperature (50 °C) under reduced pressure,
due probably to π−π stacking of the intermolecular aromatic
rings. Specifically, the aromatic ring of TEU-EP functions as an
electron donor, whereas that of 33DDS is electron deficient due
to the strong electron withdrawing sulfuryl group bonded.
Furthermore, the molecular branching of TEU-EP will decrease
its crystallization ability and further destabilize TEU-EP’s and
33DDS’s respective molecular crystal lattice in the TEU-EP/
33DDS mixture. These results suggest that TEU-EP/33DDS can
be treated as a homogeneous “single” epoxy system, which will
greatly facilitate its application. Moreover, different from viscous
DGEBA/33DDS at room temperature, TEU-EP/33DDS is a
glassy solid that can be crushed easily to fine powder, thus greatly
facilitating its handling, transport, and application, especially for
solid processing for epoxy-based molding compounds for
electronic encapsulation and powder coatings.
The intensive exothermic peak (Figure 2a) arises from the ring
opening of TEU-EP under attack of the amino group of 33DDS
according to nucleophilic addition mechanisms. TEU-EP/
33DDS shows the exothermic peak at 241 °C which is 25 °C
higher than that of DGEBA/33DDS, indicating the lower
reactivity. The decreased reactivity could be attributed to the
lower polarizability of the epoxy rings of TEU-EP, because its
−CH2Ph affects the neighboring epoxy ring less than the
−CH2OPh of DGEBA does through an electron withdrawing
effect. Other studies also highlighted that the position of the
epoxy ring could greatly influence the curing reactivity of
resulting biobased epoxy resins.52
2873
Research Article
A curing kinetic study of thermosets plays a very important
role in optimizing curing reaction cycles.33 Here the multiple
heating-rate DSC results (Figure 2b and Table 1) show that
Table 1. Onset and Peak Temperatures and Reaction Heat of
TEU-EP/33DDS Reaction System
heating rate (K/min) Tonset (°C) Tpeak (°C) reaction heat (J/g)
3 173 208 372
4.5 183 219 377
6.7 193 229 365
10 202 241 371
TEU-EP/33DDS’s exothermic curing reaction mainly occurs
over the temperature range of 150−280 °C, and the onset and
peak exothermic temperatures, Tonset and Tpeak, and fractional
conversional curves systematically shift to a higher temperature
as the heating rate increases. Nevertheless, the overall reaction
heat changes very slightly (365−377 J/g), which implies that the
cure reaction arrives at essentially the same ultimate reaction
extent. Furthermore, TEU-EP/33DDS’s normalized molar
reaction exotherm (∼100 kJ/mol epoxide) is comparable to
typical values of other epoxy-amine curing reactions.53,54
Therefore, TEU-EP can be sufficiently cured by 33DDS under
suitable curing conditions.
The data collected from conversional curves (Figure 2b) are
processed with the advanced isoconversional method55,56 to give
rise to effective activation energy, Eα; see eqs 1 and 2:
n n
I(Eα , Tα , i)βi −1
Φ(Eα) = ∑∑ = min
i=1 j≠i
I(Eα , Tα , j)βj−1 (1)
Tα ⎡ −E ⎤
I(Eα , Tα , i) = ∫T exp⎢ α ⎥ dT
⎣ RTα ⎦
α −Δα (2)
where Eα is the activation energy for a given conversion α, βi and
βj are the different heating rates, I is the temperature integral
approximated using a trapezoid rule, and Tα and Tα−Δα are the
reaction temperature for α and Δα (typically 0.02), respectively.
The effective activation energy, Eα, and averaged curing
temperature changes with α substantially (Figure 2c). As α
increases to 12%, the temperature increases from 176 to 198 °C,
and Eα increases slightly (from ∼66 to ∼69 kJ/mol). The
increased temperature leads to the increased the reaction rate,
and meanwhile engenders the rapid increase in viscosity, thus
leading to a higher energy barrier associated with the molecular
diffusion. On the other hand, the hydroxyl groups produced from
the epoxy-amine reaction can catalyze the epoxy-amine addition
via a hydroxyl-amine-epoxy complex mechanism,57 thus lowering
the energetic barrier for the ring opening reaction. These two
factors function in opposite ways, and the molecular diffusion
likely overweighs the hydroxyl catalytic effect, accounting for the
increased Eα.
A much more dramatic increase in Eα (from ∼70 to ∼100 kJ/
mol) is observed for α > 70% and the rather high curing
temperature of >230 °C, implying a significant change of reaction
mechanisms. The increase in Eα is due probably to topological
restriction for the remaining epoxy-amine reaction. In particular,
the primary amino groups (RNH2) are generally much more
reactive than the corresponding substituted secondary amine
groups (R1R2NH) to attack an epoxy ring due largely to less
steric hindrance. This difference would become more prominent
for some aromatic amine-cured epoxy systems.54 Note here that
DOI: 10.1021/acssuschemeng.6b00479
ACS Sustainable Chem. Eng. 2016, 4, 2869−2880
ACS Sustainable Chemistry & Engineering
Figure 3. (a) Storage modulus and dissipation factor (tan δ) against temperature with heating rate of 3 °C/min. (b) Dimension change against
temperature (5 °C/min) from room temperature to 250 °C. Onset softening temperatures of DGEBA/33DDS and TEU-EP/33DDS are 156 and 174
°C, respectively, and the averaged CTEs (25−140 °C) are 5.72 × 10−5 vs 5.94 × 10−5 K−1.
because the curing temperature at this stage is rather high, even
above the ultimate glass transition temperature as will be
discussed in the following subsection, diffusion controlled
reaction kinetics with lower activation energy seems less
important.58 In this case, the reaction kinetic rate-controlled
step is probably dominated by the reaction between TEU-EP’s
epoxy group and the secondary amino group derived from
33DDS. Such reactions have to surmount the higher energetic
barrier due to the much increased steric hindrance of the
substituted amino groups of 33DDS to attack the epoxy ring via
the nucleophilic addition mechanism.
An unified model-free method, eq 3,59 was used to predict the
isothermal conversion:
T
tα =
∫0 α exp ( ) dT
−Eα
RTα
β exp( )
−Eα
RT0 (3)
where T0 is the given isothermal temperature and Tα is for a
nonisothermal reaction processes to a given conversion, α, with a
constant heating rate β. Predicted conversion curves of the
isothermal curing reaction of TEU-EP/33DDS (170, 180, 190,
200, and 210 °C) are shown in Figure 2b. By applying the Flory
gelation theory,60 the gel-point conversion (αgel) of stoichio-
metric TEU-EP/33DDS is calculated to be 40.8% where epoxy
and amino functionalities are taken as 3 and 4, respectively.
Raising temperature increases from 170 to 210 °C leads to a
systematic decrease in time for αgel from 29.3 to 6.1 min. This
result implicates that in large quantity applications, it is rational
to process TEU-EP/33DDS at a relatively low temperature to
prolong the pot life, and the post cure at a higher temperature, if
necessary, could be applied to reduce the curing cycle to increase
productivity.
In addition, to give a general impression on the storage stability
of the epoxy system, we predicted the curing reaction carried out
at room temperature (20 °C) by neglecting diffusion effect at the
deep glassy state (leading to even lower curing rate). The result
indicates that TEU-EP/33DDS could reach only 4% conversion
(practically lower than this value) for 60 days, implying the
excellent storage stability. The long storage life combined with
the fast curing at a relatively high processing temperature could
enable TEU-EP/33DDS suitable for one-pot epoxy components
2874
Research Article
(e.g., green solvent-free epoxy powder coatings and epoxy
molding compounds for microelectronic encapsulation) with
easy transportation, storage, handling, and finishing.
Dynamic Mechanical Properties of Cured Epoxy. TEU-
EP/33DDS shows significantly higher storage modulus (E′) than
DGEBA/33DDS within the experimental temperature range
(Figure 3a). Even at 170 °C, TEU-EP/33DDS is still rather hard
(E′ = 2033 MPa), but DGEBA/33DDS softens (E′ = 420 MPa).
The glass transition temperature (Tg for tan δmax) of TEU-EP/
33DDS is 207 °C, 33 °C higher than that of DGEBA/33DDS
(174 °C). To the best of our knowledge, so far no biobased epoxy
resin could reach such a high Tg under conditions that such high
biobased content of the epoxy monomer (80 wt %) is used. In
this study, even in the presence of stoichiometric 33DDS, the
pure TEU-EP/33DDS system can still retain the biobased
content of 61 wt %. In addition, TEU-EP/33DDS shows a
broader glass relaxation than DGEBA/33DDS does, as indicated
by a 9 °C increase in the half peak height width of tan δ, implying
a broader range of cooperative segment motions involved in this
relaxation. The much enhanced E′ and Tg approve that TEU-EP/
33DDS possesses significantly enhanced thermomechanical
characteristics.
The enhanced thermomechanical properties stem from the
high rigidity of the triazine ring-linked eugenol structure and
higher functionalities of TEU-EP. To illustrate, akin to 33DDS
could cause its cured DGEBA with reduced free volume
(antiplastic effect),61 the evenly distributed eugenol moieties
on the triazine ring could likely reduce the free volume in cured
TEU-EP/33DDS further. In this case, the antiplastic effect in
TEU-EP/33DDS may be more pronounced, which could
respond for a more notably increased in the storage modulus
at a low temperature (38% increase in E′ at 30 °C). Once at the
rubbery state, however, although the two systems hold a
relatively constant value of rubbery E′, TEU-EP/33DDS’s E′
(∼10 MPa) is much lower than DGEBA/33DDS’s (∼21 MPa),
due probably to different contributions of the triazine-linked
eugenol and bisphenol A segments. Note here that the
determined epoxy equivalent weight of the DGEBA (188 g/
mol) and TEU-EP (222 g/mol) shows no significant difference
(<20%), but the rubbery moduli of the cured epoxy resin differ
greatly (>100%). Another reason may lie behind this finding. As
demonstrated in Scheme 3, the rotation of the aromatic ether
DOI: 10.1021/acssuschemeng.6b00479
ACS Sustainable Chem. Eng. 2016, 4, 2869−2880
ACS Sustainable Chemistry & Engineering Research Article

Scheme 3. Illustration of the Rotation of the Aromatic Rings
along the Axis Atom in TEU-EP and DGEBA Units
(−O−) will be sufficiently activated at the rubbery state and little
affected by other adjacent segments and cross-links, so that the
−O− linked eugenol rings and triazine could rotate more freely
with the increased freedom of degree. In contrast, the benzene
ring of DGEBA’s bisphenol A unit rotating along the
−C(CH3)2− linkage exhibits the decreased degree of freedom
due to the restriction of the two side methyl substituents on the
axial carbon. So it is reasonable to observe experimentally that the
bisphenol A unit causes the higher rubbery modulus for the
DGEBA/33DDS network.
Dimensional Stability of Cured Epoxy. Dimensional
stability is an important consideration for epoxy materials used in
many demanding areas, especially for electrical and electronic
(EE) applications. Dimension change of DGEBA/33DDS and
TEU-EP/33DDS from room temperature to well above the
softening temperature was evaluated based on the static thermal
mechanical analysis (TMA). The TMA curves (Figure 3b) shows
that the dimension change of the two epoxy systems increases
nearly linearly as the temperature increases up to ∼150 °C above
which the change becomes dramatic due to softening of the
materials. TEU-EP/33DDS displays a smaller accumulated
dimension change and a higher onset softening temperature
than DGEBA/33DDS does (174 vs 156 °C), approving that
TEU-EP/33DDS has the enhanced dimensional stability with
markedly elevated upper-service temperature.
In addition, we calculated the coefficient of thermal expansion
(CTE), α(T), from eq 4:
1 d L (T )
α (T ) =
L (T ) d T (4)
where α(T) is the temperature-dependent CTE, and L(T) is the
length of sample at a given temperature T. As displayed in Figure
3b, before softening, TEU-EP/33DDS expresses a lower α(T)
than DGEBA/33DDS does. For example, at 40 °C, CTE of TEU-
EP/33DDS is 7.6% lower than that of DGEBA/33DDS. More
importantly, over the temperature range of 25−140 °C (at glassy
state) the former shows a lower averaged CTE than the latter
does (5.72 × 10−5 vs 5.94 × 10−5 K−1). Judiciously selecting
epoxy matrix with low CTE and high modulus plays an important

Figure 4. Typical results from the nanoindentation measurements. (a) Load−displacement curves (9000 μN for 5 s). From the releasing segments of
load−displacement curves, Young’s modulus (E) and hardness (H) are calculated from eqs 5 and 6, respectively. The different colors represents the
different intents. Comparison of E (b) and H (c) for loading of 1, 3, 6, 9, and 12 mN. (d) Creep displacement against time up to 600 s (9 mN). DGEBA/
33DDS and TEU-EP/33DDS show an accumulated creep displacement of 135.8 ± 9.5 and 128.3 ± 8.9 nm, respectively.

2875 DOI: 10.1021/acssuschemeng.6b00479

ACS Sustainable Chem. Eng. 2016, 4, 2869−2880
ACS Sustainable Chemistry & Engineering
role in ensuring reliability of semiconductor devices encapsulated
by epoxy molding compounds (EMCs), to minimize the internal
thermal stress and cracks caused by the temperature fluctuation
when devices run, since today >80% semiconductor devices are
embedded using EMCs.62 For example, fundamental EMC
formulations usually contain not only a small fraction of an
organic epoxy binder (higher CTE) but a predominant fraction
of inorganic fillers (>80 wt %) such as silica powder having lower
CTE as well. The greater the CTE and modulus difference
between an epoxy matrix and fillers, the higher the thermal stress
developed and therefore the higher the probability of micro-
cracking which would eventually lead to the failure of EMC-
encapsulated electronic devices.
Nanoindentation Analysis. Nanoindentation was used to
examine mechanical properties of the cured epoxy by analyzing
Young’s (elastic) modulus, hardness, and creep displacement.
The typical load−displacement curves of DGEBA/33DDS and
TEU-EP/33DDS (Figure 4a) show that parallel indents
(different colors) are superimposed on each other, highlighting
the excellent reproducibility and homogeneous (isotropic)
properties of the sample. DGEBA/33DDS shows a greater
indentation depth and therefore lower resistance to the
indentation force than TEU-EP/33DDS does. To illustrate,
with a peak load of 9000 μN (for 5 s), DGEBA/33DDS, and
TEU-EP/33DDS show the maximum indentation depth (hmax)
of 1283 and 1051 nm, respectively. The lower hmax value could be
related to the highly rigid triazine-concentrated eugenol
segments of TEU-EP/33DDS that lead to the stronger chain
interaction such as π−π stacking among the aromatic rings. On
the other hand, although DGEBA contains the rigid bisphenol A
units, they are separated by a relatively flexible glycidol unit, so
that the overall rigidity of DGEBA/33DDS at room temperature
reduces.
Young’s modulus, the most important parameters character-
izing mechanical rigidity of materials, can be calculated from eq
5:63
1 1−ν 1 − νi
= +
Er E Ei (5)
where Ei and νi are Young’s modulus (1141 GPa) and Poisson’s
rate (0.07) of a diamond indenter, Er is the reduced elastic
modulus, E and ν are Young’s modulus and Poisson’s ratio of a
sample, respectively, and ν is taken as 0.35 for polymer
materials.50 Sample’s hardness (H) can be determined by
dividing the peak load (Pmax) by contact area (A), eq 6.63
Pmax
H=
A (6)
As the indentation load increases, E and H (Table 2) of the cured
epoxy decreases slightly, but tends to level off for above 9 mN.
This observation is associated with the “indentation size effect”,
resulting in a higher E and H values for a rather lower load.64
Importantly, under the same loading, TEU-EP/33DDS shows
the much higher E and H than DGEBA/33DDS dose (Figures.
4b and c). Especially, TEU-EP/33DDS shows a 39% and 55%
enhancement in E and H (9 mN), and therefore, TEU-EP/
33DDS is much more rigid and harder than DGEBA/33DDS is.
The creep behavior of the cured epoxy was evaluated over a
relatively long dwell time of 600 s (9 mN) at room temperature.
The resulting typical profiles (Figure 4d) display that the creep
displacement increases quickly initially yet the increase slows
down after 200 s. The creep displacement of TEU-EP/33DDS
2876
Research Article
Table 2. Young’s Modulus and Hardness of DGEBA/33DDS
and TEU-EP/33DDS Determined from the Nanoindentation
Measurements under Different Loadings
DGEBA/33DDS TEU-EP/33DDS
load Young’s modulus hardness Young’s modulus hardness
(mN) (GPa) (MPa) (GPa) (MPa)
1 4.45 ± 0.04 402 ± 5 6.28 ± 0.04 634 ± 7
3 4.22 ± 0.03 380 ± 5 5.90 ± 0.01 597 ± 4
6 4.16 ± 0.03 376 ± 3 5.80 ± 0.02 582 ± 4
9 4.12 ± 0.02 373 ± 2 5.74 ± 0.02 577 ± 3
12 4.10 ± 0.01 367 ± 2 5.71 ± 0.03 574 ± 4
increases slower than that of DGEBA/33DDS, with a lower
cumulative creep displacement (128.3 ± 8.9 vs 135.8 ± 9.5 nm)
at 600 s. Therefore, TEU-EP endows the cured epoxy with a
better creep resistance at room temperature, particularly within a
relatively short dwell time (<200 s). The improved creep
resistance can be attributed to more rigid molecular structure of
TEU-EP leads to the less plastic distortion of the cured epoxy
network.
To summarize, in contrast to the standard DGEBA, TEU-EP
bestows the notably improved mechanical indentation resistance,
increased Young’s modulus, surface hardness, and creep
resistance on the cured TEU-EP/33DDS system.
Broadband Dielectric Property. The dielectric properties
of DGEBA/33DDS and TEU-EP/33DDS are compared in
Figure 5 including the permittivity, ε′, (approximate to dielectric
constant k) and dielectric loss factor, ε″/ε′, over a broad
bandwidth (10−106 Hz). TEU-EP/33DDS (5.0−5.2) shows a
lower ε′ than DGEBA/33DDS (5.5−5.8) does (Figure 5a),
which means that less electric energy is absorbed by the material
subjected to the alternative electric field. This finding also
suggests that TEU-EP/33DDS may express the improved
electromagnetic wave transparency, if the material is used as
insulation materials for microwave communication, for example,
mobiles and radars. Decreased ε′ of TEU-EP/33DDS could be
explained based on the Debye equation, eq 7:65,66
k−1 4π ⎛ μ2 ⎞
= N ⎜αe + αd + ⎟
k+2 3 ⎝ 3k bT ⎠ (7)
where k, N, αe, αd, μ, kb, and T are the dielectric constant, number
density of dipoles, electric polarization, distortion polarization,
orientation polarization related to the dipole moment,
Boltzmann constant, and temperature, respectively.
For TEU-EP, the highly symmetric low polarizable triazine
ring can form a highly delocalized p−π conjugation with its
linked three eugenol moieties via the −O− bonds, resulting in
more evenly distributed electrons on dipoles and thus reduced
orientated electric polarizability, in response to the reduction in
αe and N. Moreover, the branched molecular structure of TEU-
EP could disturb the regular arrangement of dipoles in the TEU-
EP/33DDS network, so that the number density of the dipoles,
N, further decreases. Furthermore, considering the molecular
branching of TEU-EP, the chain distribution of TEU-EP/33DDS
may be more isotropic, rendering a smaller μ. As a result, the
decreased αe, N, and μ values causes lowered k and in turn ε′
values of TEU-EP/33DDS.
In addition to the lowered permittivity, TEU-EP/33DDS also
shows a lower dielectric dissipation factor (ε″/ε′) than DGEBA/
33DDS does (Figure 5b), especially in a relatively high-frequency
range (>105 Hz). Once the polarization can no longer follow the
DOI: 10.1021/acssuschemeng.6b00479
ACS Sustainable Chem. Eng. 2016, 4, 2869−2880
ACS Sustainable Chemistry & Engineering
Figure 5. (a) Permittivity, ε′, and (b) dielectric loss factor, ε″/ε′, of DGEBA/33DDS and TEU-EP/33DDS over frequency of 10 Hz-2 MHz. The
maximum ε″/ε′ values (0.027 and 0.014) appear at 6.5 × 104 Hz.
Figure 6. (a) Thermogravimetric analytical curves of cured DGEBA/33DDS and TEU-EP/33DDS from 50 to 800 °C in N2. (b) Heat release rate
(HRR)vs temperature curves from micro combination calorimeter (MCC) tests.
change of the externally applied alternative electric field, the
relaxation occurs,67 as indicated by the peak for ε″/ε′.
Importantly, TEU-EP/33DDS shows the far lower maximum
ε″/ε′ values than DGEBA/33DDS does (0.014 vs 0.027), which
indicates the less electric energy dissipated as heat. The reason
for the lowered ε″/ε′ is likely that the highly conjugated, triazine-
linked eugenol segments will greatly restrict the relaxation of the
dipoles in the TEU-EP/33DDS network, thus reducing the
dielectric polarization relaxation compared to DGEBA/33DDS.
Noticeably, the maximum ε″/ε′ of the two systems coincides at
the same frequency (6.5 × 104 Hz), implicating the same origin
of the dielectric relaxation owing to the dipole motion in the
cross-linked network, probably the sulfonyl-related dipoles from
33DDS.
As we know, epoxy based materials are widely used in
microelectronics, especially semiconductor encapsulation and
printed circuit boards. To meet the ever increasing tendency
toward miniaturization of electronics, epoxy materials with low
permittivity and low dielectric loss become very crucial to reduce
heat generation, temperature rise, energy consumption, and
electric leakage. Therefore, TEU-EP would be attractive in
electric and microelectronic areas. In addition to the improved
2877
Research Article
dielectric properties, compromising as-discussed excellent
thermomechanical properties and mechanical performances
(high Tg, ultrahigh elastic modulus and harness, improved
creep resistance, and lowered thermal expansion), we could
foresee that TEU-EP holds a high potential to replace DGEBA as
insulation materials for electrical and electronic (EE) applica-
tions.
Thermal Decomposition and Flammability of Cured
Epoxy. The thermal decomposition of TEU-EP/33DDS and
DGEBA/33DDS was comparatively studied with TGA in N2
(Figure 6a). No apparent weight loss up to 290 °C occurs, and
DGEBA/33DDS begins to decompose at a higher temperature
than TEU-EP/33DDS does. The onset decomposition of TEU-
EP/33DDS could be assigned to the dissociation of the methoxyl
groups from eugenol moieties.68 Despite that, TEU-EP/33DDS
starts to degrade at a high enough temperature above its Tg
(Figure 3a) and softening temperature (Figure 3b), so that it can
be used as a hard plastic safely. Also, TEU-EP/33DDS shows a
much lower peak decomposition rate than DGEBA/33DDS does
and affords the much higher pyrolytic (800 °C) residual (25.1%
vs 13.8%), an increment by 82%. This result is related to the
highly compact triazine-linked aromatic structure of TEU-EP
DOI: 10.1021/acssuschemeng.6b00479
ACS Sustainable Chem. Eng. 2016, 4, 2869−2880
ACS Sustainable Chemistry & Engineering
that promotes charring and reduces liberation of gaseous
products during the anaerobic pyrolysis. Noticeably, the nitrogen
on the triazine ring could enhance the char formation of the
TEU-EP/33DDS during the pyrolysis, whereas DGEBA cannot
afford any additional nitrogen atoms to promote charring of the
cured epoxy matrix.69
On the other hand, flammability is a very important
consideration for epoxy resins used as electrical and micro-
electronic materials to reduce fire risks.62 Here flammability of
the cured epoxy was examined according to the micro
combustion calorimeter (MCC) results as shown in Figure 6b
where the variation of the heat release rate (HHR) with
temperature is displayed. DGEBA/33DDS shows an intensive
exothermic peak around 370−520 °C with the peak temperature,
peak HHR and total HR values of 434 °C, 400 W/g, and 24.9 kJ/
g, respectively. TEU-EP/33DDS shows a slightly lowered
maximum exothermic temperature (409 °C) yet markedly
decreased peak HHR (191 W/g) and total HR (17.6 kJ/g), , a
reduction by 52% and 29%, respectively. These results suggest
that the gaseous combustible production is reduced notably,
consisting with the aforementioned high residual yield (Figure
6a). The MCC and TG results support the low flammability of
TEU-EP/33DDS, which is associated with the highly aromatic
nitrogen-rich triazine ring linked eugenol segments of TEU-EP.
Such highly compact aromatic rings will reduce the production of
gaseous combustible by promoting charring. In short, TEU-EP
endows the cured epoxy with the reduced flammability, hence
improving the fire safety.
■ CONCLUSIONS
A novel triazine-linked, eugenol-based epoxy resin (TEU-EP)
has been synthesized and its molecular structure has been
identified with FTIR, 1H NMR, 13C NMR, and ESI-Mass. TEU-
EP could be sufficiently cured by 3,3′-diaminodiphenyl sulfone
(33DDS). The curing kinetics analysis showed that TEU-EP/
33DDS has excellent storage stability and high-temperature
processability. In comparison with DGEBA/33DDS, TEU-EP/
33DDS expressed significantly improved thermomechanical
properties (33 °C, 39%, and 55% enhancement in the glass
transition temperature, Young’s modulus, and hardness,
respectively). TEU-EP/33DDS was also characterized by the
better creep resistance and dimensional stability, higher
softening temperature, and lower permittivity and dielectric
loss factor, as well as the much higher pyrolytic residual yield and
lowered flammability.
Due to these attractive properties, TEU-EP holds a great
potential as a sustainable alternative to satisfy more demanding
and even cutting-edge applications, in particular, in EE industries.
Extending our current work, a low-cost, scalable approach to
synthesizing TEU-EP as well as fabrication of related high-
performance nanocomposites will be of great interest in future
study. In particular, it would be very interesting and important to
work out the up-scaling of synthesis reaction of TEU-EP based
more on the principles of green chemistry and using as many
renewable/recyclable reagents as possible.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acssusche-
meng.6b00479.
2878
Research Article
FTIR spectra of TEU and TEU-EP (Figure S1), ESI-Mass
spectrum of TEU-EP (Figure S2), and DSC analytical
curves of TEU-EP and 33DDS (Figure S3) (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*Tel: +34 91 549 34 22. Fax: +34 91 550 30 47. E-mail: deyi.
wang@imdea.org.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The research leading to these results has received funding from
the European Union Seventh Framework Programme (FP7
2007-2013) under grant agreement PIIF-GA-2013-626682. In
addition, this work is partly funded by Spanish Ministry of
Economy and Competitiveness (MINECO) under Ramón y
Cajal grant (RYC-2012-10737).
■
REFERENCES
(1) May, C. A. Epoxy Resins Chemistry and Technology, 2nd ed.; Marcel
Dekker, Inc: New York, 1988.
(2) Petrie, E. M. Epoxy Adhesive Formulations; McGraw-Hill
Publishing: New York, 2006.
(3) Auvergne, R.; Caillol, S.; David, G.; Boutevin, B.; Pascault, J.-P.
Biobased Thermosetting Epoxy: Present and Future. Chem. Rev. 2014,
114, 1082−1115.
(4) Raquez, J. M.; Deléglise, M.; Lacrampe, M. F.; Krawczak, P.
Thermosetting (Bio)Materials Derived from Renewable Resources: A
Critical Review. Prog. Polym. Sci. 2010, 35, 487−509.
(5) Tan, S. G.; Chow, W. S. Biobased Epoxidized Vegetable Oils Andits
Greener Epoxy Blends: A Review. Polym.-Plast. Technol. Eng. 2010, 49,
1581−1590.
(6) Tan, S. G.; Ahmad, Z.; Chow, W. S. Relationships of Cure Kinetics
and Processing for Epoxidized Soybean Oil Bio-Thermoset. Ind. Crops
Prod. 2013, 43, 378−385.
(7) Deng, L. L.; Shen, M. M.; Yu, J.; Wu, K.; Ha, C. Y. Preparation,
Characterization, and Flame Retardancy of Novel Rosin-Based Siloxane
Epoxy Resins. Ind. Eng. Chem. Res. 2012, 51, 8178−8184.
(8) Huang, K.; Zhang, J.; Li, M.; Xia, J.; Zhou, Y. Exploration of the
Complementary Properties of Biobased Epoxies Derived from Rosin
Diacid and Dimer Fatty Acid for Balanced Performance. Ind. Crops Prod.
2013, 49, 497−506.
(9) Liu, X.; Zhang, J. High-Performance Biobased Epoxy Derived from
Rosin. Polym. Int. 2010, 59, 607−609.
(10) Aouf, C.; Nouailhas, H.; Fache, M.; Caillol, S.; Boutevin, B.;
Fulcrand, H. Multi-Functionalization of Gallic Acid. Synthesis of a
Novel Bio-Based Epoxy Resin. Eur. Polym. J. 2013, 49, 1185−1195.
(11) Aouf, C.; Lecomte, J.; Villeneuve, P.; Dubreucq, E.; Fulcrand, H.
Chemo-Enzymatic Functionalization of Gallic and Vanillic Acids:
Synthesis of Bio-Based Epoxy Resins Prepolymers. Green Chem. 2012,
14, 2328−2336.
(12) Cao, L.; Liu, X.; Na, H.; Wu, Y.; Zheng, W.; Zhu, J. How a Bio-
Based Epoxy Monomer Enhanced the Properties of Diglycidyl Ether of
Bisphenol a (Dgeba)/Graphene Composites. J. Mater. Chem. A 2013, 1,
5081−5088.
(13) Fache, M.; Darroman, E.; Besse, V.; Auvergne, R.; Caillol, S.;
Boutevin, B. Vanillin, a Promising Biobased Building-Block for
Monomer Synthesis. Green Chem. 2014, 16, 1987−1998.
(14) Fache, M.; Auvergne, R.; Boutevin, B.; Caillol, S. New Vanillin-
Derived Diepoxy Monomers for the Synthesis of Biobased Thermosets.
Eur. Polym. J. 2015, 67, 527−538.
(15) Ma, S.; Liu, X.; Jiang, Y.; Tang, Z.; Zhang, C.; Zhu, J. Bio-Based
Epoxy Resin from Itaconic Acid and Its Thermosets Cured with
Anhydride and Comonomers. Green Chem. 2013, 15, 245−254.
DOI: 10.1021/acssuschemeng.6b00479
ACS Sustainable Chem. Eng. 2016, 4, 2869−2880
ACS Sustainable Chemistry & Engineering
(16) Huang, K.; Zhang, P.; Zhang, J.; Li, S.; Li, M.; Xia, J.; Zhou, Y.
Preparation of Biobased Epoxies Using Tung Oil Fatty Acid-Derived
C21 Diacid and C22 Triacid and Study of Epoxy Properties. Green
Chem. 2013, 15, 2466−2475.
(17) Pan, X.; Sengupta, P.; Webster, D. C. High Biobased Content
Epoxy-Anhydride Thermosets from Epoxidized Sucrose Esters of Fatty
Acids. Biomacromolecules 2011, 12, 2416−2428.
(18) Chrysanthos, M.; Galy, J.; Pascault, J.-P. Preparation and
Properties of Bio-Based Epoxy Networks Derived from Isosorbide
Diglycidyl Ether. Polymer 2011, 52, 3611−3620.
(19) Feng, X.; East, A.; Hammond, W.; Ophir, Z.; Zhang, Y.; Jaffe, M.
Thermal Analysis Characterization of Isosorbide-Containing Thermo-
sets. J. Therm. Anal. Calorim. 2012, 109, 1267−1275.
(20) Chang, R.; Qin, J.; Gao, J. Fully Biobased Epoxy from Isosorbide
Diglycidyl Ether Cured by Biobased Curing Agents with Enhanced
Properties. J. Polym. Res. 2014, 21, 501.
(21) Xin, J.; Zhang, P.; Huang, K.; Zhang, J. Study of Green Epoxy
Resins Derived from Renewable Cinnamic Acid and Dipentene:
Synthesis, Curing and Properties. RSC Adv. 2014, 4, 8525−8532.
(22) Jaillet, F.; Darroman, E.; Ratsimihety, A.; Auvergne, R.; Boutevin,
B.; Caillol, S. New Biobased Epoxy Materials from Cardanol. Eur. J. Lipid
Sci. Technol. 2014, 116, 63−73.
(23) Chen, J.; Nie, X.; Liu, Z.; Mi, Z.; Zhou, Y. Synthesis and
Application of Polyepoxide Cardanol Glycidyl Ether as Biobased
Polyepoxide Reactive Diluent for Epoxy Resin. ACS Sustainable Chem.
Eng. 2015, 3, 1164−1171.
(24) Rapi, Z.; Szolnoki, B.; Bakó, P.; Niedermann, P.; Toldy, A.;
Bodzay, B.; Keglevich, G.; Marosi, G. Synthesis and Characterization of
Biobased Epoxy Monomers Derived from D-Glucose. Eur. Polym. J.
2015, 67, 375−382.
(25) Hu, F.; La Scala, J. J.; Sadler, J. M.; Palmese, G. R. Synthesis and
Characterization of Thermosetting Furan-Based Epoxy Systems.
Macromolecules 2014, 47, 3332−3342.
(26) Maiorana, A.; Spinella, S.; Gross, R. A. Bio-Based Alternative to
the Diglycidyl Ether of Bisphenol a with Controlled Materials
Properties. Biomacromolecules 2015, 16, 1021−1031.
(27) Altuna, F. I.; Ruseckaite, R. A.; Stefani, P. M. Biobased
Thermosetting Epoxy Foams: Mechanical and Thermal Character-
ization. ACS Sustainable Chem. Eng. 2015, 3, 1406.
(28) De, B.; Gupta, K.; Mandal, M.; Karak, N. Biodegradable
Hyperbranched Epoxy from Castor Oil-Based Hyperbranched Polyester
Polyol. ACS Sustainable Chem. Eng. 2014, 2, 445−453.
(29) Ma, S.; Webster, D. C. Naturally Occurring Acids as Cross-
Linkers to Yield Voc-Free, High-Performance, Fully Bio-Based,
Degradable Thermosets. Macromolecules 2015, 48, 7127−7137.
(30) Menard, R.; Negrell, C.; Fache, M.; Ferry, L.; Sonnier, R.; David,
G. From a Bio-Based Phosphorus-Containing Epoxy Monomer to Fully
Bio-Based Flame-Retardant Thermosets. RSC Adv. 2015, 5, 70856−
70867.
(31) Ma, S.; Liu, X.; Jiang, Y.; Fan, L.; Feng, J.; Zhu, J. Synthesis and
Properties of Phosphorus-Containing Bio-Based Epoxy Resin from
Itaconic Acid. Sci. China: Chem. 2014, 57, 379−388.
(32) Qin, J.; Woloctt, M.; Zhang, J. Use of Polycarboxylic Acid Derived
from Partially Depolymerized Lignin as a Curing Agent for Epoxy
Application. ACS Sustainable Chem. Eng. 2014, 2, 188−193.
(33) Roudsari, G. M.; Mohanty, A. K.; Misra, M. Study of the Curing
Kinetics of Epoxy Resins with Biobased Hardener and Epoxidized
Soybean Oil. ACS Sustainable Chem. Eng. 2014, 2, 2111−2116.
(34) El-Thaher, N.; Mussone, P.; Bressler, D.; Choi, P. Kinetics Study
of Curing Epoxy Resins with Hydrolyzed Proteins and the Effect of
Denaturants Urea and Sodium Dodecyl Sulfate. ACS Sustainable Chem.
Eng. 2014, 2, 282−287.
(35) Ding, C.; Matharu, A. S. Recent Developments on Biobased
Curing Agents: A Review of Their Preparation and Use. ACS Sustainable
Chem. Eng. 2014, 2, 2217−2236.
(36) Tachibana, Y.; Torii, J.; Kasuya, K.-i.; Funabashi, M.; Kunioka, M.
Hardening Process and Properties of an Epoxy Resin with Bio-Based
Hardener Derived from Furfural. RSC Adv. 2014, 4, 55723−55731.
2879
Research Article
(37) Harvey, B. G.; Sahagun, C. M.; Guenthner, A. J.; Groshens, T. J.;
Cambrea, L. R.; Reams, J. T.; Mabry, J. M. A High-Performance
Renewable Thermosetting Resin Derived from Eugenol. ChemSusChem
2014, 7, 1964−1969.
(38) Neda, M.; Okinaga, K.; Shibata, M. High-Performance Bio-Based
Thermosetting Resins Based on Bismaleimide and Allyl-Etherified
Eugenol Derivatives. Mater. Chem. Phys. 2014, 148, 319−327.
(39) Rojo, L.; Vazquez, B.; Parra, J.; Bravo, A. L.; Deb, S.; Roman, J. S.
From Natural Products to Polymeric Derivatives of ″Eugenol″: A New
Approach for Preparation of Dental Composites and Orthopedic Bone
Cements. Biomacromolecules 2006, 7, 2751−2761.
(40) Thirukumaran, P.; Shakila Parveen, A.; Sarojadevi, M. Synthesis
and Copolymerization of Fully Biobased Benzoxazines from Renewable
Resources. ACS Sustainable Chem. Eng. 2014, 2, 2790−2801.
(41) Thirukumaran, P.; Shakila, A.; Muthusamy, S. Synthesis and
Characterization of Novel Bio-Based Benzoxazines from Eugenol. RSC
Adv. 2014, 4, 7959−7966.
(42) Dumas, L.; Bonnaud, L.; Olivier, M.; Poorteman, M.; Dubois, P.
Eugenol-Based Benzoxazine: From Straight Synthesis to Taming of the
Network Properties. J. Mater. Chem. A 2015, 3, 6012−6018.
(43) Dai, J.; Jiang, Y.; Liu, X.; Wang, J.; Zhu, J. Synthesis of Eugenol-
Based Multifunctional Monomers Via a Thiol-Ene Reaction and
Preparation of Uv Curable Resins Together with Soybean Oil
Derivatives. RSC Adv. 2016, 6, 17857−17866.
(44) Qin, J.; Liu, H.; Zhang, P.; Wolcott, M.; Zhang, J. Use of Eugenol
and Rosin as Feedstocks for Biobased Epoxy Resins and Study of Curing
and Performance Properties. Polym. Int. 2014, 63, 760−765.
(45) Wan, J.; Gan, B.; Li, C.; Molina-Aldareguia, J. M.; Li, Z.; Wang, X.;
Wang, D.-Y. A Novel Biobased Epoxy Resin with High Mechanical
Stiffness and Low Flammability: Synthesis, Characterization and
Properties. J. Mater. Chem. A 2015, 3, 21907−21921.
(46) Wan, J.; Gan, B.; Li, C.; Molina-Aldareguia, J.; Kalali, E. N.; Wang,
X.; Wang, D.-Y. A Sustainable, Eugenol-Derived Epoxy Resin with High
Biobased Content, Modulus, Hardness and Low Flammability:
Synthesis, Curing Kinetics and Structure−Property Relationship.
Chem. Eng. J. 2016, 284, 1080−1093.
(47) Patel, N. G.; Sreeram, A.; Venkatanarayanan, R. I.; Krishnan, S.;
Yuya, P. A. Elevated Temperature Nanoindentation Characterization of
Poly(Para-Phenylene Vinylene) Conjugated Polymer Films. Polym. Test.
2015, 41, 17−25.
(48) Pharr, G. M.; Bolshakov, A. Understanding Nanoindentation
Unloading Curves. J. Mater. Res. 2002, 17, 2660−2671.
(49) Li, Y.; Rios, O.; Kessler, M. R. Thermomagnetic Processing of
Liquid-Crystalline Epoxy Resins and Their Mechanical Characterization
Using Nanoindentation. ACS Appl. Mater. Interfaces 2014, 6, 19456−
19464.
(50) Shen, L.; Wang, L.; Liu, T.; He, C. Nanoindentation and
Morphological Studies of Epoxy Nanocomposites. Macromol. Mater.
Eng. 2006, 291, 1358−1366.
(51) Paiva, A.; Sheller, N.; Foster, M. D.; Crosby, A. J.; Shull, K. R.
Microindentation and Nanoindentation Studies of Aging in Pressure-
Sensitive Adhesives. Macromolecules 2001, 34, 2269−2276.
(52) Nicolau, A.; Samios, D.; Piatnick, C. M. S.; Reiznautt, Q. B.;
Martini, D. D.; Chagas, A. L. On the Polymerisation of the Epoxidised
Biodiesel: The Importance of the Epoxy Rings Position, the Process and
the Products. Eur. Polym. J. 2012, 48, 1266−1278.
(53) Wan, J.; Li, B.-G.; Fan, H.; Bu, Z.-Y.; Xu, C.-J. Nonisothermal
Reaction Kinetics of Dgeba with Four-Armed Starlike Polyamine with
Benzene Core (Mxbdp) as Novel Curing Agent. Thermochim. Acta
2010, 510, 46−52.
(54) Rozenberg, B. A. Kinetics, Thermodynamics and Mechanism of
Reactions of Epoxy Oligomers with Amines. Adv. Polym. Sci. 1986, 75,
113−165.
(55) Vyazovkin, S. Evaluation of Activation Energy of Thermally
Stimulated Solid-State Reactions under Arbitrary Variation of Temper-
ature. J. Comput. Chem. 1997, 18, 393−402.
(56) Vyazovkin, S. Modification of the Integral Isoconversional
Method to Account for Variation in the Activation Energy. J. Comput.
Chem. 2001, 22, 178−183.
DOI: 10.1021/acssuschemeng.6b00479
ACS Sustainable Chem. Eng. 2016, 4, 2869−2880
ACS Sustainable Chemistry & Engineering Research Article

(57) Smith, I. T. The Mechanism of the Crosslinking of Epoxide Resins

by Amines. Polymer 1961, 2, 95−108.
(58) Wan, J.; Li, C.; Bu, Z.-Y.; Xu, C.-J.; Li, B.-G.; Fan, H. A
Comparative Study of Epoxy Resin Cured with a Linear Diamine and a
Branched Polyamine. Chem. Eng. J. 2012, 188, 160−172.
(59) Vyazovkin, S. A Unified Approach to Kinetic Processing of
Nonisothermal Data. Int. J. Chem. Kinet. 1996, 28, 95−101.
(60) Odian, G. Principles of Polymerization, Fourth Ed.; John Wiley &
Sons, Inc.: Hoboken, NJ, 2004.
(61) Tu, J.; Tucker, S. J.; Christensen, S.; Sayed, A. R.; Jarrett, W. L.;
Wiggins, J. S. Phenylene Ring Motions in Isomeric Glassy Epoxy
Networks and Their Contributions to Thermal and Mechanical
Properties. Macromolecules 2015, 48, 1748−1758.
(62) Kinjo, N.; Ogata, M.; Nishi, K.; Kaneda, A.; Dusek, K. Epoxy
Molding Compounds as Encapsulation Materials for Microelectronic
Devices. Adv. Polym. Sci. 1989, 88, 1−48.
(63) Oliver, W. C.; Pharr, G. M. Measurement of Hardness and Elastic
Modulus by Instrumented Indentation: Advances in Understanding and
Refinements to Methodology. J. Mater. Res. 2004, 19, 3−20.
(64) Swadener, J. G.; George, E. P.; Pharr, G. M. The Correlation of the
Indentation Size Effect Measured with Indenters of Various Shapes. J.
Mech. Phys. Solids 2002, 50, 681−694.
(65) Yuan, C.; Jin, K.; Li, K.; Diao, S.; Tong, J.; Fang, Q. Non-Porous
Low-K Dielectric Films Based on a New Structural Amorphous
Fluoropolymer. Adv. Mater. 2013, 25, 4875−4878.
(66) Volksen, W.; Miller, R. D.; Dubois, G. Low Dielectric Constant
Materials. Chem. Rev. 2010, 110, 56−110.
(67) Kim, J.-Y.; Lee, W. H.; Suk, J. W.; Potts, J. R.; Chou, H.;
Kholmanov, I. N.; Piner, R. D.; Lee, J.; Akinwande, D.; Ruoff, R. S.
Chlorination of Reduced Graphene Oxide Enhances the Dielectric
Constant of Reduced Graphene Oxide/Polymer Composites. Adv.
Mater. 2013, 25, 2308−2313.
(68) Haw, J. F.; Schultz, T. P. Carbon-13 Cp/Mas Nmr and Ft-Ir Study
of Low-Temperature Lignin Pyrolysis. Holzforschung 1985, 39, 289.
(69) Liu, H.; Wang, X.; Wu, D. Novel Cyclotriphosphazene-Based
Epoxy Compound and Its Application in Halogen-Free Epoxy
Thermosetting Systems: Synthesis, Curing Behaviors, and Flame
Retardancy. Polym. Degrad. Stab. 2014, 103, 96−112.

2880 DOI: 10.1021/acssuschemeng.6b00479

ACS Sustainable Chem. Eng. 2016, 4, 2869−2880