Bio-based thermosetting resins composed of aliphatic polyol-derived polymaleimides and allyleugenol

Article abstract of DOI:10.1016/j.reactfunctpolym.2015.10.009

Bio-based bismaleimide (2MPD), trismaleimide (3MGC) and tetramaleimide (4MDG) were synthesized by reactions of 4-isocyanatophenylmaleimide with 1,3-propanediol, glycerol and α,α′-diglycerol, respectively. Although 2MPD did not melt until the temperature w

Full text of DOI:10.1016/j.reactfunctpolym.2015.10.009

Bio-based thermosetting resins composed of aliphatic polyol-derived poly-
maleimides and allyleugenol
Mitsuhiro Shibata, Toshiaki Shimasaki, Hiroyuki Satoh, Misaki Iwai,
Makiyo Neda
PII:
S1381-5148(15)30057-2
DOI:
Reference:
doi: 10.1016/j.reactfunctpolym.2015.10.009
REACT 3576
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Revised date:
Accepted date:
20 July 2015
15 October 2015
16 October 2015
Please cite this article as: Mitsuhiro Shibata, Toshiaki Shimasaki, Hiroyuki Satoh, Misaki
Iwai, Makiyo Neda, Bio-based thermosetting resins composed of aliphatic polyol-derived
polymaleimides and allyleugenol, (2015), doi: 10.1016/j.reactfunctpolym.2015.10.009
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ACCEPTED MANUSCRIPT
Bio-based thermosetting resins composed of aliphatic polyol-derived
polymaleimides and allyleugenol
Mitsuhiro Shibata,* Toshiaki Shimasaki, Hiroyuki Satoh, Misaki Iwai, Makiyo Neda
Department of Life and Environmental Sciences, Faculty of Engineering,
Chiba Institute of Technology, 2-17-1, Tsudanuma, Narashino, Chiba 275-0016, Japan
*Corresponding author. Tel.:+81 47 478 0423; fax:+81 47 478 0423.
E-mail address: mitsuhiro.shibata@p.chibakoudai.jp (M. Shibata)
URL: http://www.le.it-chiba.ac.jp/env-org/index.html (M. Shibata)
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ABSTRACT
Bio-based bismaleimide (2MPD), trismaleimide (3MGC) and tetramaleimide (4MDG)
were synthesized by reactions of 4-isocyanatophenylmaleimide with 1,3-propanediol,
glycerol and α,α’-diglycerol, respectively. Although 2MPD did not melt until the
temperature where thermal decomposition starts, 3MGC and 4MDG exhibited broad
melting temperatures with onset points at 165 °C and 124 °C, respectively. 3MGC and
4MDG
were
homogeneously
prepolymerized
at
170
°C
with
2,4-diallyl-6-methoxyphenol (rAEG) which was prepared by the Claisen rearrangement
of allyl-etherified eugenol (AEG). The prepolymers were compression-molded at
250 °C to produce cured rAEG/3MGC (A3Mxy) and rAEG/4MDG (A4Mxy) with the
allyl/maleimide ratio of x/y = 1/1, 1/2 or 1/3. The FT-IR analysis revealed that the ene
reaction of allyl and maleimide groups and subsequent addition copolymerization
occurred for the cured resins. The thermal and mechanical properties of the cured resins
were compared with those of the cured rAEG/4,4'-bismaleimidodiphenylmethane (BMI)
(ABMxy) with the same allyl/maleimide ratio. A3M13 and A4M13 showed no
inflection point of thermal expansion due to glass transition until 300 °C, which is a
little lower than the thermo-degradation temperature. Flexural strengths and flexural
strains at break for A3Ms and A4Ms increased with the polymaleimide contents, and
those of A3M13 and A4M13 were much higher than those of ABM13.
Keywords: glycerol; diglycerol; 1,3-propanediol; polymaleimide; thermosetting resins
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1. Introduction
Development of bio-based polymers, i.e., polymers from renewable feedstock, has been
driven by the growing concerns of long-term sustainability and negative impacts on the
environment of petroleum-based polymer materials. So far, bio-based thermoplastic
polymers such as polylactides, polyhydroxyalkanoates, polyamide 11 and cellulose
esters have shown great potential to replace the petrochemical thermoplastics in many
applications [1-4]. In recent years, effective utilization of renewable feedstock has
increasingly penetrated thermosetting resins and their composites [5-8]. For example,
soybean oil [9-11], glycerol [12,13], polyglycerol [14], sorbitol [15,16], isosorbide
[17,18] and cardanol [19,20] etc. have been successfully utilized to the syntheses of
epoxy resins. Vegetable oils [21-24], terpenes [25], fumaric acid and sebacic acid [26]
etc. have been utilized to the syntheses of unsaturated polyester, vinylester and alkyd
resins. However, these bio-based thermosetting resins mainly derived from aliphatic
renewable feedstock were difficult to be used to the applications such as electronics and
structural materials requiring excellent thermal and mechanical properties.
Thermosetting resins based on allylphenolic-bismaleimide blend are an important class
of high-performance thermosetting polymers [27]. Among them, a commercial
high-performance thermosetting resin, Matrimid® 5292 (Huntsman Corp., former Ciba
Specialty Chemicals Corp.), based on 2,2’-diallybisphenol
A
(DABA)
/
4,4’-bismaleimidodiphenylmethane (BMI) is one of the leading matrix resins in carbon
fiber composites for advanced aerospace application (Scheme 1) [28]. The flexural
modulus (4.06 GPa) and 5% weight loss temperature (T5: > 450 °C) of the cured
DABA/BMI resin with the molar ratio of 1/1 are much higher than those (2.30 GPa and
284 °C) of the glycerol-based epoxy resin cured with diethyltoluenediamine
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(DETDA) and those (2.12 GPa and 370°C) of the bisphenol-A-based epoxy resin cured
with DETDA [13,28]. FT-IR analysis of cured DABA/BMI resin has shown its
formation to proceed by an ene reaction followed by addition copolymerization [29,30].
Recently, we reported that BMI resins cured with eugenol (EG), bieugenol (BEG:
3,3'-dimethoxy-5,5'-diallyl-1,1'-biphenyl-2,2'-diol) or eugenol novolac (EGN) showed
superior thermal and mechanical properties [31]. Furthermore, it was shown that BMI
resins cured with allyl-etherified EG (AEG) or allyl-etherified BEG (ABEG) exhibited
superior glass transition temperature (Tg) and T5 that were higher than 350 °C and
450 °C, respectively [32]. When the bio-based allylphenolic compounds are combined
with bio-based polymaleimides derived from industrially important renewable aliphatic
polyols [33], it is expected that bio-based cured resins having much better thermal and
mechanical properties than the already reported bio-based epoxy and unsaturated
polyester resins are produced.
In this study, bismaleimide (2MPD), trismaleimide (3MGC) and tetramaleimide
(4MDG) were synthesized by reactions of 4-isocyanatophenylmaleimide (ICPM) with
1,3-propanediol (PD), glycerol (GC) and α,α’-diglycerol (DG) as bio-based aliphatic
polyols, respectively. The bio-based polymaleimides having aliphatic ether frameworks
are expected to be more flexible than BMI, leading to the improvement of brittleness.
In addition, especially for the tris- and tetra-maleimides, it is expected that the heat
resistance is not so largely reduced because of the higher maleimide functionality than
BMI. As a bio-based allylphenolic compound combining with the bio-based
polymaleimides, Claisen-rearranged AEG (rAEG, 2,4-diallyl-6-methoxyphenol) was
used in this study (Scheme 2). Regarding the ene reaction of allyl and maleimide
groups, it is expected that rAEG has a higher reactivity than AEG, because it is known
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that o-allylphenol has a higher reactivity toward N-phenylmaleimide than allyl phenyl
ether [34]. The present study describes the synthesis of 2MPD, 3MGC and 4MDG,
and thermal and mechanical properties of cured rAEG/3MGC resins (A3Ms) and cured
rAEG/4MDG resins (A4Ms) as compared with those of cured rAEG/BMI resins
(ABMs) which have not been previously reported (Scheme 3).
2. Experimental
2.1. Materials
Eugenol (EG, purity > 98.0% by gas chromatography) and cyclopentyl methyl ether
(CPME) were purchased from Wako Pure Chemical Industries, Ltd. (Osaka, Japan).
,’-Diglycerol (DG) was supplied from Sakamoto Yakuhin Kogyo, Co. Ltd. (Osaka,
Japan).
4,4’-Bismaleimidodiphenylmethane (BMI) and triphenylphosphine (TPP)
were purchased from Tokyo Kasei Kogyo Co. Ltd. (Tokyo, Japan). 1,3-Propanediol
(PD), glycerol (GC), n-hexanol, allyl bromide, sodium hydroxide, hydroquinone (HQ),
1,4-diazabicyclo[2.2.2]octane (DABCO) and dimethyl sulfoxide (DMSO) were
purchased from Kanto Chemical Co., Inc. (Tokyo, Japan). All the commercially
available
reagents
were
used
without
further
purification.
N-[(4-azidocarbonyl)phenyl]maleimide (ACPM) was synthesized according to the
procedures described earlier [35]. rAEG was also synthesized according to the
procedures described earlier (Scheme 3) [32].
2.2. Synthesis of 1,3-bis[N-(p-maleimidophenyl)carbamoyloxy]propane (2MPD)
To a solution of ACPM (10.0 g, 44.0 mmol) in CPME (400 mL), HQ (100 mg) and
DABCO (20 mg) were added under a nitrogen atmosphere. After the contaminated
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water was azeotropically removed by refluxing the solution at 120 °C for 30 min, a
solution of PD (1.52 g, 20.0 mmol) in anhydrous DMF (100 mL) was added and stirred
at 80 °C for 24 h. n-Hexanol (7 mL, 57 mmol) was added to the reaction mixture and
stirred at 50 °C for 3 h in order to quench excess isocyanate which was produced from
ACPM. After the reaction mixture was concentrated in vacuo, the viscous liquid was
slowly added to diethyl ether (400 mL) under stirring. The formed precipitate was
filtered and dried in vacuo at room temperature for 24 h to give 2MPD as a yellow
powder (yield: 6.8 g, 67 %). MALDI-TOF-MS (m/z): calcd. for C25H20N4O8+Na
527.12, found 526.93.
2.3. Synthesis of 1,2,3-tris[N-(p-maleimidophenyl)carbamoyloxy]propane (3MGC)
To a solution of ACPM (7.53 g, 33.0 mmol) in CPME (400 mL), HQ (75 mg) and
DABCO (20 mg) were added under a nitrogen atmosphere. After the contaminated
water was azeotropically removed by refluxing the solution at 120 °C for 30 min, a
solution of GC (0.921 g, 10 mmol) in anhydrous DMF (100 mL) was added and stirred
at 80 °C for 24 h. n-Hexanol (5 mL, 41 mmol) was added to the reaction mixture and
stirred at 50 °C for 3 h. After the reaction mixture was concentrated in vacuo, the
viscous liquid was slowly added to diethyl ether (400 mL) under stirring. The formed
precipitate was filtered and dried in vacuo at room temperature for 24 h to give 3MGC
as a yellow powder (yield: 5.7 g, 77 %). MALDI-TOF-MS (m/z): calcd. for
C36H26N6O12 + Na 757.15, found 757.63.
2.4. Synthesis of 1,2,6,7-tetra[N-(p-maleimidophenyl)carbamoyloxy]-4-oxaheptane
(4MDG)
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To a solution of ACPM (10.0 g, 44.0 mmol) in CPME (500 mL), HQ (100 mg) and
DABCO (25 mg) were added under a nitrogen atmosphere. After the contaminated
water was azeotropically removed by refluxing the solution at 120 °C for 30 min, a
solution of DG (1.66 g, 10.0 mmol) in anhydrous DMF (125 mL) was added and stirred
at 80 °C for 24 h. n-Hexanol (6 mL, 60 mmol) was added to the reaction mixture and
stirred at 50 °C for 3 h. After the reaction mixture was concentrated in vacuo, the
viscous liquid was slowly added to diethyl ether (500 mL) under stirring. The formed
precipitate was filtered and dried in vacuo at room temperature for 24 h to give 4MDG
as a yellow powder (yield: 9.0 g, 88 %). MALDI-TOF-MS (m/z): calcd. for
C50H38N8O17 + Na 1045.23, found 1045.75.
2.5. Preparation of cured polymaleimide resins
A typical preparation method of the cured 3MGC (c3MGC) is as follow: A mixture of
3MGC (1.40 g, 1.90 mmol) and TPP (7 mg) was pulverized in a mortal. The pulverized
mixture was compression-molded at 210 °C/8 MPa for 1 h, 220 °C/8 MPa for 2 h, and
finally 250 °C/8 MPa for 5 h using Mini Test Press-10 (Toyo Seiki Co., Ltd, Tokyo,
Japan) to produce c3MGC. The thickness of the molded plate was controlled using a
stainless steel spacer (thickness: 1.0 mm) during the compression molding. The cured
4MGC (c4MGC) was prepared by a similar procedure. The curing conditions of
c3MGC and c4MGC are summarized in Table 1.
2.6. Preparation of cured rAEG/polymaleimide resins
A typical preparation method of the cure rAEG/3MGC resin with the feed molar ratio of
1/1 (A3M11) is as follow: A mixture of rAEG (0.612 g, 3.00 mmol) and 3MGC (2.20 g,
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3.00 mmol) was melt-mixed at 170 °C and then gradually heated to 200 °C over 1 h to
produce
a
gelatinous material. The pre-polymer that was obtained was
compression-molded at 210 °C/8 MPa for 1 h, 220 °C/8 MPa for 2 h, and finally
250 °C/8 MPa for 5 h to produce A3M11. Sample codes and curing conditions of all
the cured rAEG/polymaleimide resins are also summarized in Table 1.
2.7. Measurements
Proton nuclear magnetic resonance (1H-NMR) spectra were recorded on a Bruker
AV-400 (400 MHz) (Madison, WI, USA) using DMSO-d6 as a solvent. FT-IR spectra
were measured on a FTIR 8100 spectrometer (Shimadzu Co. Ltd., Kyoto, Japan) by the
KBr or attenuated total reflectance (ATR) methods. Matrix-assisted laser desorption/
ionization time-of-flight (MALDI-TOF) mass spectra were recorded with a
SHIMADZU AXIMA Performance mass spectrometer with 2,5-dihydroxybenzoic acid
(DHBA) as a matrix. The differential thermal analysis (DTA) of the sample (15-20
mg) was performed on a Shimadzu DTA-50 instrument at a heating rate of 10 °C min-1
in a nitrogen atmosphere. Thermomechanical analysis (TMA) of a square-shaped
specimen (5 × 5 × 1 mm3) was conducted on a TMA-60 (Shimadzu Co., Ltd.) at a
heating rate of 10 °C min-1 in a nitrogen atmosphere. The Tg was determined from the
intersect of tangents at the two points with a significant change in coefficient of thermal
expansion (CTE). The T5 of the sample (10-15 mg) was measured over the temperature
range of room temperature to 500 °C on a Shimadzu TGA-50 thermogravimetric
analyzer at a heating rate of 20°C min-1 in a nitrogen atmosphere. Flexural testing of the
rectangular specimen (50 × 7 × 1 mm3) was performed using an Autograph AG-1
(Shimadzu Co., Ltd.) based on the standard method for testing the flexural properties of
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plastics (JIS K7171: 2008 (ISO 178: 2001)). The span length was 30 mm, and the
testing speed was 10 mm min-1. Five specimens were tested for each set of samples,
and the mean value and standard deviation were calculated.
3. Results and discussion
3.1. Synthesis and characterization of 2MPD, 3MGC and 4MDG
First, we examined a direct esterification reaction of p-carboxyphenylmaleimide
(CPMI) and PD or GC using dicyclohexylcarbodiimide as a condensation reagent, and
two-step esterification via acid chloride of CPMI. However, we could not produce a
pure esterified polymaleimide in a good yield. Therefore, the carboxy group of CPMI
was converted to isocyanate group in order to enhance the reactivity toward hydroxy
group. Synthesis routes of 2MPD, 3MGC and 4MDG are shown in Scheme 4. The
synthetic procedure essentially involves addition reaction of a bio-based polyol and
4-(maleimido)phenyl isocyanate (MPIC). The MPIC was in situ generated by thermal
Curtius rearrangement of ACPM, which was synthesized by the reaction of CPMI and
diphenyl phosphoryl azide essentially according to the procedure described in the
literature [34]. The carbon atom contents derived from renewable PG, GC and DGC
for 2MPG, 3MGC and 4MDG were calculated to be 7.1, 4.9 and 7.1 wt%, respectively.
Currently, several strategies are envisioned to produce bio-based maleic anhydride
(MAH) from renewable resources such as bio-based succinic acid, crotonic acid and
xylose [36-38]. If their processes are established, CPMI can be prepared from
4-aminobenzoic acid and the bio-based MAH. In such a case, the carbon atom
contents derived from renewable resources (PD, GC, DG and MAH) for 2MPD, 3MGC
and 4MDG are expected to be increased to 26.2, 24.5 and 25.8%, respectively.
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Fig. 1 shows the 1H-NMR spectra of 2MPD, 3MGC and 4MDG in DMSO-d6. The
1H signals at 9.82 (s, 1H), 7.59 (m, 2H), 7.25 (m, 2H) and 7.15 ppm (s, 2H) for 2MPD
were assigned to Hd, Hb, Hc and Ha of the N-maleimidophenylcarbamoyloxy group,
1
respectively. Also, the H signals at 4.28 (m, 4H) and 2.05 ppm (m, 2H) were assigned
to He and Hf of the 1,3-propanedioxy group, respectively. 3MGC and 4MDG displayed
1
1
similar H-signal pattern for the N-maleimidophenylcarbamoyloxy groups. The H
signals of Hf and He of the glycerol moiety of 3MGC were observed at 5.32 (m, 1H) and
1
4.52-4.05 (m, 4H), respectively. The H signals of Hf, He and Hg of the diglycerol
moiety of 4MDG were observed at 5.23 (m, 2H), 4.6-4.0 (m, 4H) and 4.0-3.4 ppm (m,
4H), respectively. The 1H signal patterns of He and Hg became complex, because there
are two sets of diastereomers (RS = SR and RR; RS = SR and SS) having different
spectroscopic response for 4MDG due to the presence of two asymmetric carbons (Cf)
and one symmetry plane.
Fig. 2 shows FT-IR spectra of 2MPD, 3MGC and 4MDG. The absorption band
due to N-H stretching () of formed urethane bond was observed at 3337 cm–1. The
urethane (C=O) band overlapped with maleimide (C=O) band at 1707 cm–1. All the
polymaleimides showed two absorption bands characteristic to maleimide group at 833
cm–1 and 689 cm–1, which are attributed to out-of-plane bending (fmaleimide=C–H
and deformation () of maleimide ring [39]. These two bands characteristic to
maleimide group were used for the check of progress of curing reaction of maleimide
and allyl groups.
3.2. Thermal properties of 2MPD, 3MGC and 4MDG
Fig. 3 shows TG-DTA curves of 2MPD, 3MGC and 4MDG. The onset temperatures of
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thermal degradation for 2MPD, 3MGC and 4MDG were 220.3, 223.0 and 213.9 °C,
respectively. 2MPD showed no endothermic peak due to melting until the onset
degradation temperature. 3MGC and 4MDG started to melt at around 165 and 124 °C,
respectively, which were lower than the onset degradation temperature. 3MGC
displayed a melting peak-top temperature (Tm) at 214.3 °C and did not show an
exothermic peak due to addition homopolymerization of maleimide group until the
onset degradation temperature.
4MDG showed double melting peaks at 137.2 and
179.2 °C and an exothermic peak at 207.0 °C, which was close to the onset degradation
temperature (213.9 °C). The fact that 4MDG showed double melting peaks may be
related to the presence of diastereomers.
Fig. 4 shows DTA curves of 2MPD, 3MGC and 4MDG with 0.5 wt% TPP as a
catalyst for anionic polymerization [40]. When 0.5 wt% TPP was added, an
exothermic peak of 4MDG became 200.2 °C, which was lower than the onset
degradation temperature, indicating that 4MDG with TPP can be thermally cured at
around 200 °C. Although an exothermic peak of 3MGC with TPP was 228.5 °C which
was still higher than the onset degradation temperature (223.0 °C), the onset exothermal
temperature (200 °C) was lower than the onset degradation temperature, indicating that
3MGC with TPP can be cured at around 200-220 °C. Actually, 3MGC and 4MDG
with 0.5 wt% TPP could be thermally cured at the curing process of 210 °C/1 h,
220 °C/2 h and 250°C/5 h to produce c3MGC and c4MDG as brown plates. Table 2
summarizes the TMA and TGA data of c3MGC and c4MDG. Both c3MGC and
c4MDG showed no inflection points of TMA curves due to glass transition until 300 °C.
T5s of c3MGC and c4MDG were 359 °C and 372 °C, which were much higher than
those (254.8 °C and 257.3°C) of 3MGC and 4MDG, respectively.
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3.3. Curing reaction of rAEG and 3MGC or 4MDG
3MGC and 4MDG were prepolymerized with rAEG at the molar ratio of 1/1, 1/2 or 1/3
at 170-200 °C, and compression-molded at 210 °C/1 h, 220 °C/2 h and 250 °C/5 h to
produce A3M11, 12 or 13 and A4M11, 12 or 13. Fig. 5 shows FT-IR spectra of A3Ms,
A4Ms, c3MGC and c4MDG as compared with rAEG, In the spectrum of rAEG, the
absorption bands due to the allyl (C=C) and (=C–H) were observed at 1637 cm–1 and
991, 908 cm–1, respectively. The corresponding bands characteristic of allyl group were
non-existent for A3Ms and A4Ms. The maleimide ring  band at 689 cm–1 which was
observed for 3MGC or 4MDG was almost non-existent for each cured resin. Although
the maleimide (=C–H) band at 833 cm–1 of each cured resin was weaker than that of
3MGC or 4MDG, the band considerably remained even after curing. This result may
be explained by the fact that the band at 833 cm–1 includes benzene ring (=C–H) band
which does not change by curing in addition to maleimide (=C–H) band. If the ene
reaction of eugenol and maleimide moiety occurs, succinimide-substituted isoeugenol
moiety should be produced. The propenyl (=C–H) band of trans-isoeugenol is
observed at 963 cm-1. However, no clear absorption band related to the propenyl
(=C–H) band at around 960-970 cm-1 was appeared for A3Ms or A4Ms, suggesting that
the propenyl group formed by the ene reaction of allyl group and maleimide group
further reacted with maleimide group after curing at 250 °C [31,32]. It was revealed
from the FT-IR analysis that most of the allyl and maleimide groups reacted for A3Ms
or A4Ms. Similarly, it was confirmed that most of the allyl and maleimide groups
reacted for ABMs, although their FT-IR spectra are not shown in Figure 5. Probable
reaction scheme of rAEG with 3MGC, 4MDG or BMI is shown in Scheme 5. Thus,
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the ene reaction of the allyl and maleimide groups generates an ene adduct whose
propenylidene moiety copolymerizes with maleimide group to produce a polymer
network. Although we did not depict another probable reactions, the addition
copolymerization of the original allyl and maleimide groups, and the Diels-Alder
reaction of the ene adduct and maleimide group, and subsequent ene-reaction with the
maleimide group are not excluded, as we had previously elucidated for the curing
reaction of EG and BMI [31].
3.4. Properties of the cured resins
Fig. 6 shows TMA curves of all the cured resins. Coefficient of thermal expansion
(CTE) between 100 and 200 °C and Tg measured from the TMA curve were also
summarized in Table 2. Although A4M11, A4M12 and A3M11 displayed Tgs at 232,
266 and 277 °C, respectively, other cured resins with higher maleimide contents showed
no inflection point in thermal expansion curve until 300 °C. The Tgs of the cured
resins were much higher than the Tgs (86 and 65 °C) obtained from tan  peak
temperatures of dynamic mechanical curves of tetrafunctional pentaerythritol- and
trifunctional glycerol-based epoxy resins cured with DETDA [13]. The CTEs of cured
resins decreased with increasing maleimide content, and c4MDG and c3MGC had
CTEs lower than 20 ppm.
Fig. 7 shows TGA curves of all the cured resins. It is obvious that c4MDG and
c3MGC have much higher thermal degradation temperatures than A4Ms and A3Ms,
respectively. Table 2 summarized T5s measured by the TGA curves. The T5s of A4Ms
and A3Ms increased with increasing maleimide contents, and A4M13 and A3M13
showed the highest values (323 and 336 °C), which were higher than the previously
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reported T5s (291 and 284 °C) of the pentaerythritol- and glycerol-based epoxy resins
cured with DETDA [13]. When the cured resins with the same molar ratio were
compared, although there were little difference in T5s between A4Ms and A3Ms, A4Ms
and A3Ms had much lower T5s than ABMs did. This result is attributable that the former
contain aliphatic and urethane linkages with a lower heat resistance than diphenyl
methane moiety of the later.
Fig. 8 shows flexural properties of A4Ms and A3Ms as compared with those of
ABMs. Although flexural moduli of ABMs slightly increased with increasing BMI
contents, the flexural strengths and strains at break did not increase, indicating an
increase of BMI content caused enhancement of brittle character. On the contrary,
flexural strengths and flexural strains at break for A4Ms or A3Ms increased with 4MDG
or 3MGC contents, respectively, indicating an increase of 4MDG or 3MGC content
caused enhancement of toughness. The difference should be attributed to the fact that
4MDG and 3MGC have more flexible diglycerol and glycerol moieties than a diphenyl
methane moiety of BMI. Consequently, A4M13 and A3M13 exhibited much higher
flexural strengths (109.5 and 93.0 MPa) and flexural strains at break (2.06 and 2.30%)
than ABM13 did (59.3 MPa and 1.34%). In addition, flexural moduli (3.01 and 3.48
GPa) of A4M13 and A3M13 were comparable to that of ABM13 (3.41 GPa). Also,
flexural strengths and moduli of A4M13 and A3M13 were much higher than the
previously reported flexural strengths (85.9 and 85.8 MPa) and moduli (2.50 and 2.30
GPa) of the pentaerythritol- and glycerol-based epoxy resins cured with DETDA,
respectively [13].
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4. Conclusions
2MPD, 3MGC and 4MDG were synthesized by reactions of MPIC with PD, GC and
DG, respectively. Although 2MPD did not melt until the temperature where thermal
decomposition starts, 3MGC and 4MDG exhibited broad Tms with onset points at
165 °C and 124 °C, respectively. In this study, 3MGC and 4MDG except 2MPD were
cured with rAEG at 250 °C, and the thermal and mechanical properties of A3Ms and
A4Ms were compared with those of ABMs. The Tgs and T5s of A3Ms and A4Ms
increased with increasing polymaleimide contents, and these values were higher than
those of the already reported cured materials of glycerol- and polyglycerol-based epoxy
resins. However, T5s of A3Ms and A4Ms were much lower than those of ABMs.
Flexural strengths and flexural strains at break for A3Ms and A4Ms increased with
polymaleimide contents, and those of A3M13 and A4M13 were much higher than those
of ABM13. Consequently, the bio-based allylphenolic-polymaleimide resins derived
from GC, DG and EG displayed much better thermal and mechanical properties than the
aliphatic polyol-based epoxy resins. This bio-based resin system is suited for the
applications which need a moderate heat resistance lower than 300 °C. In case of the
uses which need much higher heat resistance, rAEG/BMI resin system is preferred.
Acknowledgements
We gratefully acknowledge financial support from the Chiba Institute of Technology.
We thank Dr. Naozumi Teramoto of our department for his helpful suggestions.
References
[1] S. Apprich, Ö. Tirpanalan, J. Hell, M. Reisinger, S. Böhmdorfer, S.
15

ACCEPTED MANUSCRIPT
Siebenhandl-Ehn, S. Novalin, W. Kneifel, Wheat bran-based biorefinery 2:
Valorization of products, LWT-Food Sci. Technol. 56 (2014) 22-31.
[2] P. F. H. Harmsen, M. M. Hackmann, H. L. Bos, Green building blocks for
bio-based plastics, Biofuel Bioprod. Bior. 8 (2014) 306-324.
[3] R. Mülhaupt, Green polymer chemistry and bio-based plastics: Dreams and reality,
Macromol. Chem. Phys. 214 (2013) 159-174.
[4] M. M. Reddy, S. Vivekanandhan, M. Misra, S. Bhatia, A. K. Mohanty, Biobased
plastics and bionanocomposites: Current status and future opportunities, Prog.
Polym. Sci. 38 (2013) 1653-1689.
[5] A. Effendi, H. Gerhauser, A.V. Bridgwater, Production of renewable phenolic resins
by thermochemical conversion of biomass: A review, Renew. Sustain. Energy Rev.
12 (2008) 2092-2116.
[6] J. R. Kim, S. Sharma, The development and comparison of bio-Thermoset plastics
from epoxidized plant oils, Ind. Crop. Prod. 36 (2012) 485-499.
[7] J. M. Raquez, M. Deléglise, M. F. Lacrampe, P. Krawczak, Thermosetting
(bio)materials derived from renewable resources: A critical review, Prog. Polym.
Sci. 35 (2010) 487-509.
[8] J. C. Ronda, G. Lligadas, M. Galià, V. Cádiz, A renewable approach to
thermosetting resins, React. Funct. Polym. 73 (2013) 381-395.
[9] T. Takahashi, K. Hirayama, N. Teramoto, M. Shibata, Biocomposites composed of
epoxidized soybean oil cured with terpene-based acid anhydride and cellulose
fibers, J. Appl. Polym. Sci. 108 (2008) 1596-1602.
[10]A. P. Gupta, S. Ahmad, A. Dev, Development of novel bio-based soybean oil epoxy
resins as a function of hardener stoichiometry, Polym. Plast. Technol. Eng. 49
16

ACCEPTED MANUSCRIPT
(2010) 657-661.
[11]S. G. Tan, Z. Ahmad, W. S. Chow, Relationships of cure kinetics and processing
for epoxidized soybean oil bio-thermoset, Ind. Crop. Prod. 43 (2013) 378-385.
[12]M. Shibata, N. Teramoto, Y. Takada, S.Yoshihara, Preparation and properties of
biocomposites composed of glycerol-based epoxy resins, tannic acid, and wood
flour, J. Appl. Polym. Sci. 118 (2010) 2998-3004.
[13]P. Niedermann, G. Szebényi, A. Toldy, Novel high glass temperature sugar-based
epoxy resins: Characterization and comparison to mineral oil-based aliphatic and
aromatic resins, Express Polym. Lett. 9 (2015) 85-94.
[14]Y. Takada, K. Shinbo, Y. Someya, M. Shibata, Preparation and properties of
bio-based epoxy montomorillonite nanocomposites derived from polyglycerol
polyglycidyl ether and ε-polylysine, J. Appl. Polym. Sci. 113 (2009) 479-484.
[15]M. Shibata, S. Yoshihara, M. Yashiro, Y. Ohno, Thermal and mechanical properties
of sorbitol-based epoxy resin cured with quercetin and the biocomposites with
wood flour, J. Appl. Polym. Sci. 128 (2013) 2753-2758.
[16]M. Shibata, N. Teramoto, S. Yoshihara, Y. Itakura, Preparation and properties of
biocomposites composed of sorbitol-based epoxy resin, tung oil-pyrogallol resin
and wood flour, J. Appl. Polym. Sci. 129 (2013) 282-288.
[17]M. Chrysanthos, J. Galy, J. P. Pascault, Preparation and properties of bio-based
epoxy networks derived from isosorbide diglycidyl ether, Polymer 52 (2011)
3611-3620.
[18]J. Łukaszczyk, B. Janicki, M. Kaczmarek, Synthesis and properties of isosorbide
based epoxy resin, Eur. Polym. J. 47 (2011) 1601-1606.
[19]S. P. Huo, G. M. Wu, J. Chen, G. F. Liu, Z. W. Kong, Curing kinetics of lignin and
17

ACCEPTED MANUSCRIPT
cardanol based epoxy resin with methyl tetrahydrophthalic anhydride, Thermochim.
Acta 587 (2014) 18-23.
[20]A. Devi, D. Srivastava, Studies on the blends of cardanol-based epoxidized novolac
type phenolic resin and carboxyl-terminated polybutadiene (CTPB), I., Mater. Sci.
Engn. 458 (2007) 336-347.
[21]E. F. Assanvo, P. Gogoi, S. Dolui, S. D. Baruah, Synthesis, characterization, and
performance characteristics of alkyd resins based on Ricinodendron heudelotii oil
and their blending with epoxy resins, Ind. Crops Prod. 65 (2015) 293-302.
[22]C. Liu, L. Li, W. Lei, Y. Zhou, Development of biobased unsaturated polyester resin
containing highly functionalized castor oil, Ind. Crop. Prod. 52 (2014) 329-337.
[23]S. Miao, P. Wang, Z. Su, S. Zhang, Vegetable-oil-based polymers as future
polymeric biomaterials, Acta Biomater. 10 (2014) 1692-1704.
[24]F. S. Güner, Y. Yağcı, A. T. Erciyes, Polymers from triglyceride oils, Prog. Polym.
Sci. 31 (2006) 633-670.
[25]X. Yang, S. Li, J. Xia, J. Song, K. Huang, M. Li, Novel renewable resource-based
UV-curable copolymers derived from myrcene and tung oil: Preparation,
characterization and properties, Ind. Crop. Prod. 63 (2015) 17-25.
[26]W. X. Guo, Z. L. Shi, K. Ling, Y. L. Liu, X. H. Chen, W. Li, New unsaturated
polyesters as injectable drug carriers, Polym. Degrad. Stabl. 92 (2007) 407-413.
[27]C. P. R. Nair, Advances in addition-cure phenolic resins, Prog. Polym. Sci. 29
(2004) 401-498.
[28]J. J. King, M. Chaudhari, S. Zahir, A new bismaleimide system for high
performance applications, 29th SAMPE Symposium 29 (1984) 392-403.
[29]R. J. Morgan, E. E. Shin, B. Rosenberg, A. Jurek, Characterization of the cure
18

ACCEPTED MANUSCRIPT
reactions of bismaleimide composite matrices, Polymer 38 (1997) 639-646.
[30]B. A. Rozenberg, E. A. Dzhavadyan, R. Morgan, E. Shin, High-performance
bismaleimide matrices: cure kinetics and mechanism, Polym. Adv. Technol. 13
(2002) 837-844.
[31]M. Shibata, N. Teramoto, A. Imada, M. Neda, S. Sugimoto, Bio-based
thermosetting bismaleimide resins using eugenol, bieugenol and eugenol novolac,
React. Funct. Polym. 73 (2013) 1086-1095.
[32]M. Neda, K. Okinaga, M. Shibata, High-performance bio-based thermosetting
resins based on bismaleimide and allyl-etherified eugenol derivatives, Mater. Chem.
Phys. 148 (2014) 319-327.
[33]A. Gandini, T. M. Lacerda, From monomers to polymers from renewable resources:
recent
advances,
Prog.
Polym.
Sci.
in
press.
doi:10.1016/j.progpolymsci.2014.11.002
[34]T. Enoki, T. Takeda, K. Ishii, Effects of catalysts on the model reactions of several
maleimide resin systems (III): allyl-modified maleimide, High Performance Polym.
7 (1995) 399-410.
[35]T. Ikeda, D. Oikawa, T. Shimasaki, N. Teramoto, M. Shibata, Organogelation
behavior, thermal and mechanical properties of polymer network formed by the
Diels-Alder reaction of furan- and maleimide-terminated four-arm star-shaped
ε-caprolactone oligomers, Polymer 54 (2013) 3206-3216.
[36]J. Becker, A. Lange, J. Fabarius, C. Wittmann, Top value platform chemicals:
bio-based production of organic acids, Curr. Opin. Biotech. 36 (2015) 168-175.
[37]M. R. Z. Mamat, H. Ariffin, M. A. Hassan, M. A. K. M. Zahari, Bio-based
production of crotonic acid by pyrolysis of poly(3-hydroxybutyrate) inclusions, J.
19

ACCEPTED MANUSCRIPT
Clean. Prod., 83 (2014) 463-472.
[38]T. Ghaznavi, C. Neagoe, G. S. Patience, Partial oxidation of D-xylose to maleic
anhydride and acrylic acid over vanadyl pyrophosphate, Biomass Bioenerg., 71
(2014) 285-293.
[39]C. Gaina, V. Gaina, Synthesis and characterization of novel organotin carboxylate
maleimide monomers and copolymers, eXPRESS Polym. Lett. 3 (2009) 352-358.
[40]S. Shibahara, T. Enoki, T. Yamamoto, J. Motoyoshiya, S. Hayashi, Curing reactions
of bismaleimide resins catalyzed by triphenylphosphine. High resolution solid-state
13C NMR study, Polym. J. 28 (1996) 752-757.
20

ACCEPTED MANUSCRIPT
Table 1 Sample codes of cured resins, compostions of the feed monomers and catalyst,
and the curing conditions.
Sample
code
Feed
Molar
ratio
Curing
catalyst
(TPP)
Curing condition
monomers
Prepoly-
Compression
molding
merization
A4M11 rAEG/4MDG
A4M12 rAEG/4MDG
A4M13 rAEG/4MDG
1/1
1/2
1/3
-
-
210°C/8 MPa/1 h,
220°C/8 MPa/2 h,
250 °C/8 MPa/5 h
-
170-200 °C/1 h
-
c4MDG
4MDG
0.5 wt%
-
A3M11 rAEG/3MGC
A3M12 rAEG/3MGC
A3M13 rAEG/3MGC
1/1
1/2
1/3
-
-
210°C/8 MPa/1 h,
220°C/8 MPa/2 h,
250 °C/8 MPa/5 h
-
170-200 °C/1 h
-
c3MGC
ABM11
ABM12
ABM13
3MGC
0.5 wt%
-
rAEG/BMI
rAEG/BMI
rAEG/BMI
1/1
1/2
1/3
-
-
-
210°C/8 MPa/1 h,
220°C/8 MPa/2 h,
250 °C/8 MPa/5 h
170-200 °C/1 h
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Table 2 Tgs and CTEs mesaured by TMA and T5s measured by TGA for A4Ms, A3Ms
and ABMs.
Sample code
A4M11
A4M12
A4M13
c4MDG
A3M11
A3M12
A3M13
c3MGC
ABM11
ABM12
ABM13
Tg (°C)
232
CTE*1 (ppm)
143.1
74.4
T5 (°C)
309
266
315
>300
>300
277
52.2
323
19.0
359
79.9
308
>300
>300
>300
>350
>350
>350
48.0
316
37.8
336
12.3
372
42.7
463.3
487.9
497.8
50.7
41.4
*1 CTE (coefficient of thermal expansion) between 100 and 200 °C.
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Figure and scheme captions
Scheme 1. Conventional allylphenolic-maleimide resin.
Scheme 2. Synthetic route of rAEG.
Scheme 3. Chemical structures of 2MPD, 3MGC and 4MDG, and abbreviations of the
cured resins in this study. *1 x/y is a molar ratio of allyl/maleimide (x/y = 1/1, 1/2 or
1/3).
Scheme 4. Synthetic routes of 2MPD, 3MGC and 4MDG.
Scheme 5. Probable reaction mechanism for rAEG and polymaleimides.
Fig. 1. 1H-NMR spectra of 2MPD, 3MGC and 4MDG in DMSO-d6.
Fig. 2. FT-IR spectra of 2MPD, 3MGC and 4MDG.
Fig. 3. TG-DTA curves of 2MPD, 3MGC and 4MDG.
Fig. 4. DTA curves of 2MPD, 3MGC and 4MDG with 0.5 wt% TPP.
Fig. 5. FT-IR spectra of rAEG, 4MDG, A4Ms, c4MDG, 3MGC, A3Ms and c3MGC.
Fig. 6. TMA curves of A4Ms, c4MDG, A3Ms and c3MGC.
Fig. 7. TGA curves of A4Ms, c4MDG, A3Ms and c3MGC.
Fig. 8. Flexural properties of A4Ms, A3Ms and ABMs.
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Fig. 1
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Fig. 2
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Fig. 3
26

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Fig. 4
27

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Fig. 5
28

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Fig. 6
29