Reactive & Functional Polymers 73 (2013) 1086–1095

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Reactive & Functional Polymers

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Bio-based thermosetting bismaleimide resins using eugenol, bieugenol

and eugenol novolac
Mitsuhiro Shibata ⇑, Naozumi Tetramoto, Ayumi Imada, Makiyo Neda, Shimon Sugimoto
Department of Life and Environmental Sciences, Faculty of Engineering, Chiba Institute of Technology, 2-17-1 Tsudanuma, Narashino, Chiba 275-0016, Japan

a r t i c l e i n f o a b s t r a c t

Article history: 5,50 -Bieugenol (BEG) and eugenol novolac (EGN) were synthesized by the oxidative coupling reaction of
Received 23 February 2013 eugenol (EG) and the addition–condensation reaction of EG with formaldehyde, respectively. The EG, BEG
Received in revised form 26 March 2013 and EGN were prepolymerized with 4,40 -bismaleimidediphenylmethane (BMI) at 180 °C and then com-
Accepted 1 May 2013
pression-molded at finally 250 °C for 6 h to produce cured EG/BMI (EB), BEG/BMI (BB) and EGN/BMI
Available online 10 May 2013
(NB) resins with eugenol/maleimide unit ratios of 1/1, 1/2 and 1/3. The FT-IR analysis of EBs and 13C
NMR analysis of the model reaction product of EG/N-phenylmaleimide (PMI) 1/3 at 200 °C for 12 h sug-
Keywords:
gested that the ene reaction and subsequent Diels-Alder/ene reactions mainly occurred for EBs. The FT-IR
Renewable resources
Eugenol
analyses of BBs and NBs supported the occurrence of ene reaction and subsequent thermal addition copo-
Bismaleimide lymerization in a similar manner to the well-known curing reaction of 2,20 -diallylbisphenol A and BMI.
Thermosetting resins The glass transition temperature (Tg) and 5% weight loss temperature (T5) of the cured resin increased
Reaction mechanism with increasing BMI content, and EB 1/3 showed the highest Tg 377 °C and T5 475 °C. The flexural
strengths and moduli of EBs and NBs were higher than those of BBs, and EB 1/2 showed the most bal-
anced flexural strength and modulus (84.5 MPa and 2.75 GPa). The FE-SEM analysis revealed that there
is no phase separation for all the cured resins.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction
In recent years, renewable resources-derived polymers (bio-
based polymers) are attracting a great deal of attention because
of the advantages of these polymers such as conservation of lim-
ited petroleum resources, the control of carbon dioxide emissions
that lead to global warming [1–4], and possible biodegradability.
Most recently, much focus is being placed on bio-based thermoset-
ting resins such as epoxy resins, phenol resins, unsaturated polyes-
ter resins and their composites, because these materials are hard to
be recycled due to the infusible and insoluble properties [5–9].
Petroleum-based thermosetting bismaleimide resins are used as
the matrix resins for multilayer printed circuit boards and ad-
vanced composite materials in the aerospace industry [10–15].
For example, a commercial thermosetting bismaleimide resin,
Matrimid 5292 (Ciba-Geigy, Basel, Switzerland), based on 2,20 -dial-
lylbisphenol A (DABA)/4,40 -bismaleimidediphenylmethane (BMI)
is one of the leading matrix resins in carbon fiber composites for
advanced aerospace application [13]. The FT-IR analysis of the
cured DABA/BMI resin has shown that a stepwise ene reaction
and subsequent chain polymerization in addition to an etherifica-
tion reaction occur for DABA/BMI [14,15]. Eugenol (EG, 4-allyl-2-
methoxyphenol) is a main component (80 wt%) of clove oil. The
⇑ Corresponding author. Tel.: +81 47 478 0423; fax: +81 47 478 0439.
E-mail address: shibata@sky.it-chiba.ac.jp (M. Shibata).
fact that EG is relatively cheap (ca. $5 kg1) [16] makes it an eco-
nomically realistic feedstock for the synthesis of bio-based alterna-
tives of DABA. Although EG is widely used in perfumes,
antioxidants, drugs, foods and taste items [17,18], there have been
little investigations on the utilization of EG for polymer materials.
As a derivative of EG, 5,50 -bieugenol (BEG, dehydrodieugenol, 3,30 -
dimethoxy-5,50 -di-2-propenyl-1,10 -biphenyl-2,20 -diol) was synthe-
sized by the oxidative coupling reaction of EG [19,20]. Eugenol
novolac (EGN) was also synthesized by the addition-condensation
reaction of EG with formaldehyde [21]. However, the utilization of
BEG and EGN for polymer materials has not yet been reported. In
this study, EG, BEG and EGN are cured with BMI, and thermal
and mechanical properties of the cured resins are investigated
(Schemes 1 and 2). Also, the FT-IR analysis of the cured resins
and 13C NMR analysis of the model reaction product of EG and
N-phenylmaleimide (PMI) was performed in order to elucidate
the curing mechanism.
2. Experimental
2.1. Materials
Eugenol (EG, purity >98.0% by gas chromatography),
N-phenylmaleimide (PMI), 4,40 -bismaleimidediphenylmethane
(BMI) and 37% formaldehyde aqueous solution (formalin)
were purchased from Tokyo Kasei Kogyo Co. Ltd. (Tokyo, Japan).

1381-5148/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.reactfunctpolym.2013.05.002
 M. Shibata et al. / Reactive & Functional Polymers 73 (2013) 1086–1095 1087

Scheme 1. Synthetic schemes of BEG and EGN.

Scheme 2. Chemical structures of PMI and BMI.

Potassium hexacyanoferrate was purchased from Kanto Chemical

Co., Inc. (Tokyo, Japan). All the commercially available reagents
were used without further purification.

2.2. Synthesis of 5,50 -bieugenol (BEG)

BEG was prepared from EG following a procedure previously re-

ported [19,20]. To a solution of EG (52.5 g, 0.320 mol) in a mixture
of acetone (510 mL) and deionized water (255 mL) was added 25–
27.9% aqueous ammonia (340 mL) and the mixture was stirred for
10 min. To the mixture was dropwise added a solution of potas-
sium hexacyanoferrate (105.4 g, 0.320 mol) in deionized water
(120 mL) over a period of about 5 h at room temperature and then
25–27.9% aqueous ammonium hydroxide (340 mL) was added.
After the mixture was stirred for an additional 24 h at room tem-
perature, the reaction mixture was neutralized with 10% hydro-
chloric acid and allowed to stand for 1 h. The formed precipitate
was filtered, washed with deionized water and ethanol, and then
dried in vacuo at 60 °C for 24 h to give BEG as white powder
(31.3 g) in 60% yield.

2.3. Synthesis of eugenol novolac (EGN)

To a solution of eugenol (82.1 g, 0.500 mol), acetic acid (25 mL)

and hydrochloric acid (25.0 mL) was dropwise added formalin
(33.5 g, 0.375 mol) and the mixture was stirred for 95 °C for 6 h.
The formed viscous brown liquid was separated by decantation
and dissolved in acetone (70 mL). To the acetone solution was
added deionized water (350 mL), and the viscous brown liquid Fig. 1. 1H NMR spectra of BG, BEG and EGN in CDCl3.
1088 M. Shibata et al. / Reactive & Functional Polymers 73 (2013) 1086–1095

Fig. 2. FD-MS spectrum of EGN.

formed again was separated by decantation. The same procedure
was furthermore twice repeated, and the obtained viscous brown
liquid was dried in vacuo at 65 °C for 24 h to give EGN as viscous
brown liquid (76.1 g, 85%). The number-average molecular
weight (Mn) and weight-average molecular weight (Mw) measured
by GPC for EN were 310 and 730, respectively. The molecular
weight (516.62) of the EN with a degree of polymerization (DP)
of 3 was used for the calculation of a feed amount of EGN,
based on the fact that m/z 516 was the strongest peak of FD-MS
for EGN.
2.4. Model reaction of EG/PMI
A mixture of EG (0.240 g, 1.46 mmol) and PMI (0.760 g,
4.38 mmol) was stirred at 200 °C for 12 h using Q-Tube pressure
reactor (Sigma–Aldrich Corp., St. Louis, MO) to give a model reac-
tion product of EG/PMI with a molar ratio of 1/3 (EP13). The
EP13 was used for the 13C NMR measurement.
2.5. Preparation of the cured resins of EG/BMI, BEG/BMI and EGN/BMI
A mixture of EGN (24.6 g, eugenol unit: 143 mmol) and BMI
(25.6 g, 71.5 mmol) was stirred at 180 °C for 2 h to produce a gelat-
inous material. The pre-polymer that was obtained was compres-
sion-molded at 200 °C/8 MPa for 1 h, 210 °C/8 MPa for 2 h, and
finally 250 °C/8 MPa for 6 h using Mini Test Press-10 (Toyo Seiki
Co., Ltd., Tokyo, Japan) to produce a cured EGN/BMI with euge-
nol/maleimide ratio of 1/1 (NB11). In a manner similar to the prep-
aration of NB11, the cured resins of EGN/BMI with eugenol/
maleimide ratios of 1/2 and 1/3 (NB12 and NB13) were also pre-
pared. Similarly, the cured resins of EG/BMI with eugenol/malei-
mide ratios of 1/1, 1/2 and 1/3 (EB11, EB12 and EB13) were also
prepared.
2.6. Measurements
Field desorption mass spectra (FD-MS) of EGN were measured
on a JMS-700 MStation equipped with a carbon emitter (JEOL

Fig. 3. FT-IR spectra of EG, EB11, EB12, EB13 and BMI.

 M. Shibata et al. / Reactive & Functional Polymers 73 (2013) 1086–1095 1089

Ltd., Tokyo, Japan) under the following conditions: ionization
method, positive FD; cathode voltage, 8.0 kV; scanning range, m/z
10–3000. Gel permeation chromatography (GPC) of EGN was car-
ried out at 40 °C on a Shimadzu LC-10A series apparatus equipped
with TSKgel G2000HHR  2 + G1000HHR  2 GPC columns (Tosoh
Corp., Tokyo, Japan) and a reflective index detector. Tetrahydrofu-
ran (THF) was used as an eluent at a flow rate of 1.0 mL min1.
Polystyrene standards with a narrow distribution of molecular
weight (Mw: 266–5970) were used for molecular weight calibra-
tion. FT-IR spectra were measured on a FTIR 8100 spectrometer
(Shimadzu Co. Ltd., Kyoto, Japan) by the KBr or attenuated total
reflectance (ATR) methods. Carbon-13 nuclear magnetic resonance
(13C NMR) spectrum was recorded on a Bruker AV-400 (400 MHz)
(Madison, WI) using CDCl3 as a solvent. The morphology of the
fractured surfaces of the cured resins after flexural tests was ob-
served by field emission-scanning electron microscopy (FE-SEM),

Fig. 4. FT-IR spectra of BB, BB11, BB12, BB13 and BMI.

Fig. 5. FT-IR spectra of NB, NB11, NB12, NB13 and BMI.

1090 M. Shibata et al. / Reactive & Functional Polymers 73 (2013) 1086–1095

using a Hitachi S-4700 machine (Hitachi High-Technologies Cor-
poration, Tokyo, Japan). The temperature at which 5% weight
loss occurred (T5) was measured on a thermogravimetric ana-
lyzer TGA7 (PerkinElmer Japan Co. Ltd., Yokohama, Japan) in a
nitrogen atmosphere at a heating rate of 20 °C min1. Dynamic
mechanical analysis (DMA) of the rectangular plates (length
30 mm, width 5 mm, thickness 0.5 mm) was performed on a
Rheolograph Solid instrument (Toyo Seiki Co., Ltd., Tokyo, Japan)
under air atmosphere with a chuck distance of 20 mm, a fre-
quency of 1 Hz and a heating rate of 2 °C min1, based on ISO
6721-4:1994 (Plastics – Determination of dynamic mechanical
properties, Part 4: Tensile vibration  Non-resonance method).
Glass transition temperature (Tg) was determined from the tan
d peak temperature. Flexural testing of the rectangular specimen
(50  10  2 mm3) was performed using an Autograph AG-1
(Shimadzu Co., Ltd.) based on the standard method for testing
the flexural properties of plastics (JIS K7171: 2008 (ISO 178:
2001)). The span length was 30 mm, and the testing speed was
10 mm min1. Five specimens were tested for each set of sam-
ples, and the mean values were calculated.

Scheme 3. Reaction mechanism for AP/PMI.

 M. Shibata et al. / Reactive & Functional Polymers 73 (2013) 1086–1095 1091

3. Results and discussion
3.1. Synthesis and characterization of BEG and EGN
Fig. 1 shows the 1H NMR spectra of EG, BEG and EGN in CDCl3.
The 1H signals at 5.98 (m, 1H), 5.10 (m, 2H) and 3.37 ppm (m, 2H)
for EG are assigned to the protons, H-g, H-h and H-f attached to al-
lyl group of EG, respectively. The corresponding allyl protons for
BEG and EGN were also observed at similar chemical shift regions.
In case of EGN, the proton of H-g00 and H-h00 were appeared as broad
signals because of the oligomeric mixtures. The benzene ring pro-
tons of EG were observed at 6.90 (m, 1H, H-a) and 6.72 ppm (m,

Scheme 4. Probable reaction mechanism for EG and BMI.

13
Fig. 6. C NMR spectrum of EP13 in CDCl3.
1092 M. Shibata et al. / Reactive & Functional Polymers 73 (2013) 1086–1095

2H, H-b,c). Two kind of aromatic 1H signals were observed for BEG
at 6.79 (m, 2H, H-b0 ) and 6.71 ppm (m, 2H, H-c0 ) based on the
occurrence of oxidative coupling reaction at C-a position. The aro-
matic 1H signals of EGN composed of two sharp signals (6.70 (s, H-
b00 ) and 6.51 ppm (s, H-c00 )) and complex signals around
6.7–6.3 ppm (broad m, weak). Those signal patterns should be
attributed to the addition-condensation reaction at the ortho posi-
tion (C-a) of hydroxy group where is the most reactive site for the
electrophilic substitution reaction, and subsequent reaction at
C-c or C-b (ortho or para position of methoxy group). The proton
signals of methoxy group was observed at 3.9 ppm for EG, BEG
and EGN. In case of EGN, the methoxy 1H signals overlapped with
methylene 1H signals at 3.9–3.7 ppm (m).
Fig. 2 shows FD-MS spectrum of EGN. The m/z peaks at 340, 516,
692 and 868 correspond to the chemical formula with n = 1, 2, 3
and 4 shown in Fig. 2. Among them, the m/z peak at 516 (n = 2)
was the strongest. Therefore, the degree of polymerization (DP)
of eugenol expressed by n + 1 for EGN is from 2 to 5, and the main
component is the EGN with DP 3. The Mn and Mw measured by GPC
for EGN were 310 and 730, whose values correspond to the EGN

Scheme 5. Probable reaction mechanisms for BEG/BMI and EGN/BMI.

Fig. 7. FE-SEM images of EBs, BBs and NBs.

 M. Shibata et al. / Reactive & Functional Polymers 73 (2013) 1086–1095 1093

Fig. 8. DMA curves of EBs.

Fig. 9. DMA curves of BBs and NBs.

with DPs 1.8 and 4.2, respectively. Regarding other m/z peaks, the
peaks at 328 and 504 are presumed to be EGN(n = 1) – C [or 2EG]
Table 1
and EGN(n = 2) – C [or EGN(n = 1) + EG], respectively. Also, the
Tg’s mesaured by DMA and T5’s measured by TGA for EBs, BBs and NBs.
peaks at 412 and 764 are presumed to be EGN(n = 2)  C7H4O [or
EGN(n = 1) + OCH3 + CH2CH@CH2] and EGN(n = 4)  C7H4O [or Sample Tg (°C) T5 (°C)

EGN(n = 3) + OCH3 + CH2CH@CH2], respectively. Those peaks EB11 256.4 433.5

should be ascribed to the fragment ions of EGN or the reacted ones EB12 345.8 464.2
EB13 377.0 477.5
in the mass chamber as the corresponding chemical species are
BB11 201.2 423.1
thought to be unstable. BB12 285.8 419.0
BB13 336.1 431.0
NB11 319.3 411.8
3.2. Curing mechanism of EG/BMI, BEG/BMI and EGN/BMI NB12 343.7 434.1
NB13 365.1 447.3

Figs. 3–5 show FT-IR spectra of the EG/BMI 1/1, 1/2, 1/3 (EB11,
12, 13), BEG/BMI 1/1, 1/2, 1/3 (BB11, 12, 13) and EGN/BMI 1/1, 1/2,
1/3 (NB11, 12, 13) resins cured at finally 250 °C, respectively. In the
spectra of EG, BEG and EGN, the absorption bands due to the allyl
C@C stretching and @CH out-of-plane bending vibrations were ob-
served at 1636–1637 cm1 and 991–995, 908 cm1, respectively.
In the spectra of BMI, the absorption bands due to the maleimide
@CH out-of-plane bending and maleimide framework vibration
were observed at 837 cm1 and 720 cm1. These bands related to
allyl and maleimide groups almost disappeared for all the cured
resins. If the ene reaction of eugenol and maleimide moiety occurs,
succinimide-substituted isoeugenol moiety should be produced.
The absorption band of propenyl @CH out-of-plane bending vibra-
tion of trans-isoeugenol is observed at 963 cm1. However, no clear
absorption band related to the propenyl @CH out-of-plane bending
vibration at around 960–970 cm1 was appeared for EBs, BBs and
NBs, suggesting that the propenyl group formed by the ene reac-
tion of allyl group and maleimide group further reacted with
maleimide group after curing at 250 °C. It was revealed from the
FT-IR analysis that most of the allyl and maleimide groups reacted
for EBs, BBs and NBs.
From the past analyses on the reaction products of 2-allylphe-
nol (AP) and N-phenylmaleimide (PMI) at 180–200 °C by Mass
and NMR spectroscopy, it was reported that AP/PMI 1/1 and 1/3
adducts are produced through the ene reaction and sequential
Diels–Alder (DA) reactions in addition to the formation of addition
copolymer, and that the AP/PMI 1/3 adduct formed by the ene–
DA–DA reactions thermally rearranges to generate the compound
with cyclohexenone moiety as is shown in Scheme 3 [22,23]. It
was also proposed that another AP/PMI 1/3 adduct might be
formed according to the re-aromatization caused by the ene reac-
tion of PMI and AP/PMI 1/2 ene–DA adduct [24,15]. Regarding the
reaction of EG and PMI, the formation of 1/1 and 1/3 adducts in
addition to copolymerized product was elucidated from the result
of Mass spectral analysis [25]. Probable reaction scheme of EG and
BMI estimated from their past studies and our FT-IR result is
1094 M. Shibata et al. / Reactive & Functional Polymers 73 (2013) 1086–1095
shown in Scheme 4. First, the ene reaction of EG and PMI produces
trans-rich 1/1 ene adduct, which undergoes DA reaction to gener-
ate reactive 1/2 ene–DA adducts. In this case, two regio-isomers
(1/2 ene–DA adduct 1 and 1/2 ene–DA adduct 2) are possible.
The formed 1/2 ene–DA adducts immediately rearomatize by the
subsequent ene reaction with PMI to give 1/3 ene–DA–ene ad-
ducts. If the 1/2 ene–DA adduct undergoes DA reaction with PMI,
the 1/3 ene–DA–DA adducts with a-methoxy carbonyl moiety is
formed by the keto-enol tautomerism. As reaction path other than
reaction mechanism shown in Scheme 4, addition copolymeriza-
tions of PMI with EG and/or 1/1 ene adduct are considered. In order
to estimate whether the 1/3 ene–DA–ene or ene–DA–DA adducts
mainly formed for the reaction of EG and BMI, 13C NMR spectrum
of the model reaction product (EB13) of EG and PMI at a molar ratio
of 1/3 at 200 °C for 12 h was measured. As was shown in Fig. 6, the
13
C signals at 146–145 ppm, 142–130 ppm and 121–109 ppm are
assigned to methoxy/hydroxy-, alkyl- and hydrogen-attached ben-
zene ring carbons in the guaiacyl moiety, respectively. Also, the 13C
signal of the methoxy carbon in the gauiacyl moiety was observed
at 54.2 ppm. The 13C signals of carbonyl and phenyl groups in N-
phenylsuccinimide moiety were observed at 176–172 ppm and
130.0, 127.7, 124.7 ppm, respectively. The 13C signal at 44.1 ppm
was reasonably assigned to the methine carbons in N-phenylsuc-
cinimide moiety formed by the DA reaction [23]. The 13C signals
of aliphatic methine and methylene carbons in succinimide-substi-
tuted alkyl moiety formed by the ene reaction were observed at
41–28 ppm. These observations support the formation of the 1/3
ene–DA–ene adducts. If 1/3 ene–DA–DA adducts produce, 13C
signals of the carbonyl moiety generating by the keto-enol
Fig. 10. TGA curves of EBs, BBs and NBs.
tautomerism should be observed at around 200–220 ppm. The fact
that no signal was observed at the near chemical shift region sug-
gests that 1/3 ene–DA–DA adducts did not produce.
On the other hand, it is known that the reaction of DABA with
PMI at 250 °C proceed stepwise ene addition reaction of allyl group
to maleimide group and consecutive/parallel vinyl copolymeriza-
tion of maleimide and propenyl groups generated by the first ene
reaction from the 13C NMR and FD-MS analyses [26]. It was also
elucidated that the curing reaction of DABA and BMI proceed in a
similar manner to that of DABA and PMI [15]. This difference in
reactivity for AP/PMI and DABA/PMI (DABA/BMI) was attributed
to steric repulsion of DABA. A similar steric repulsion is considered
for the reactions of BEG/BMI and EGN/BMI. Probable reaction
scheme of BEG/BMI and EGN/BMI estimated from those past stud-
ies and our FT-IR result is shown in Scheme 5. Thus, allyl group of
BEG or EGN reacts with maleimide group of BMI to give the ene ad-
duct with propenylidene moiety. The formed propenylidene moi-
ety copolymerizes with the maleimide group of BMI. Also, the
homo- and copolymerization of the allyl group of BEG or EGN
and the maleimide group of BMI are not excluded.
3.3. Properties of EG/BMI, BEG/BMI and EGN/BMI
Fig. 7 shows FE-SEM images of the fracture surface of EBs, BBs
and NBs. All the cured resins did not show any phase separation,
suggesting that EG, BEG and EGN certainly reacted with BMI. Figs. 8
and 9 show DMA curves of EBs, BBs and NBs. Tan d peak tempera-
ture corresponding to Tg for all the cured resins increased with
increasing BMI content (Table 1). What NB11 had the highest Tg
(319.3 °C) among the cured resins with the eugenol/maleimide
unit ratio of 1/1 may be attributed to the fact that a multifunctional
EGN molecule can react with several maleimide units. On the other
Fig. 11. Flexural properties of EBs, BBs and NBs.
 M. Shibata et al. / Reactive & Functional Polymers 73 (2013) 1086–1095
hand, EB12 and EB13 showed the highest Tg’s (345.8 and 377.0 °C)
among the cured resins with the eugenol/maleimide unit ratios of
1/2 and 1/3, respectively. This result may be related to the fact that
a EG molecule can react with several maleimide units by the
sequential ene–DA–ene reactions. The decline of storage modulus
(E0 ) was not identified until 320 °C for EBs and NBs with the euge-
nol/maleimide unit ratios of 1/2 and 1/3, indicating highly cross-
linked polyimide resins with superior heat resistance are obtained.
Fig. 10 shows TGA curves of EBs, BBs and NBs. The T5’s for all the
cured resins except BB12 increased with increasing BMI content.
All the cured resins showed the excellent T5’s higher than 400 °C
(Table 1). When the cured resins with the same unit ratio of euge-
nol/maleimide are compared, EBs had higher T5’s than BBs and NBs
did.
Fig. 11 shows flexural properties of EBs, BBs and NBs. The flex-
ural moduli of EBs and NBs slightly increased with increasing BMI
content. When the samples with the same eugenol/maleimide unit
ratio were compared, the flexural modulus and strength of EB were
comparable to those of NB, considering the error bars of flexural
properties. All the BBs except for BB12 showed much inferior flex-
ural strength and modulus than EBs and NBs did. EB12 had the
most balanced flexural strength and modulus (84.5 MPa and
2.75 GPa). The fact that NB showed better flexural properties than
BB should be related to a higher crosslinking density of NB than BB
coming from a higher allyl functionality of EGN than BEG, consid-
ering that almost all the allyl groups of EGN and BEG reacted as is
obvious from the FT-IR results. Also, the fact that EBs showed the
most balanced flexural properties in spite of the monomeric struc-
ture should be related to that eugenol can undergo the ene reaction
and sequential DA–ene reactions. Regarding the comparison with
already developed petroleum-based bismaleimide resins, the Tg
of EB12 was higher than the reported value (310 °C) of the
DABA/BMI 1/1.2 cured at 250 °C for 6 h, while the flexural strength
and modulus of EB12 were lower than the reported values
(192 MPa and 4.14 GPa) of DABA/BMI 1/1.2 [10].
4. Conclusions
BEG and EGN were synthesized by the oxidative coupling reac-
tion of EG and the addition–condensation reaction of EG with
formaldehyde, respectively. The FD-MS analysis of EGN revealed
that the oligomer with DP 3 is mainly produced. The FT-IR analysis
of EBs and 13C NMR analysis of EP13 revealed that the ene reaction
of the allyl and maleimide groups produces the 1/1 ene adduct
with succinyl propenylidene moiety, which is subsequently trans-
formed to the 1/3 ene–DA–ene adducts by the sequential DA and
ene reactions. On the other hand, the FT-IR analyses of BBs and
NBs supported the occurrence of ene reaction and subsequent ther-
mal addition copolymerization in a similar manner to the well-
known curing reaction of DABA and BMI. The FE-SEM observation
1095
revealed that there is no phase separation for all the cured resins.
The Tg and T5 of the cured resin increased with increasing BMI con-
tent. The Tg’s of EBs and NBs with the eugenol/maleimide unit ra-
tios of 1/2 and 1/3 were higher than the reported value of DABA/
BMI 1/1.2. All the cured resins showed the excellent T5’s higher
than 400 °C. Flexural moduli of EBs and NBs were 2–3 GPa, which
were higher than those of BBs. Flexural strengths of EBs were high-
er than those of NBs and BBs, and EB12 showed the highest value
(84.5 MPa).
Acknowledgement
We thank Mr. Ryusuke Osada of Material Analysis Center of our
university for assisting in measuring FE-SEM.
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