Chapter 19
Study of a Cardanol-Based Benzoxazine as
Reactive Diluent and Toughening Agent of
Conventional Benzoxazines
Pietro Campaner,* Daniele D’Amico,{ Luigia Longo,{ Cristina Stifani,{ Antonella Tarzia,{,1 and Selena Tiburzio*
*Cimteclab S.p.A., Area Science Park, Padriciano 99, 34012, Trieste, Italy
{
Cimteclab S.p.A., Zona Industriale, SP 362, 73010, Soleto (Lecce), Italy
1
Corresponding author: E-mail: antonella.tarzia@cimteclab.it
1. INTRODUCTION
Benzoxazine resins have gained significant attention in the
past few years because they combine the thermal properties
and flame retardance of phenolic resins with the mechanical
performance, excellent process ability, and wide design flex-
ibility of advanced epoxy resins [1–7]. They can be also pro-
duced from low-cost raw materials and, like epoxies, are easy
to manufacture. In addition, benzoxazines offer many advan-
tages compared with epoxies, and other chemical structures, as
they are halogen-free (epichlorohydrin is not used during their
synthesis), exhibit better flame-resistance and electrical prop-
erties than epoxies, and are characterized by an excellent high
temperature resistance and low water absorption values. With
this combination of properties, benzoxazines hold great
promise for performing in applications such as composites,
coatings, adhesives, encapsulants, and others.
Even if benzoxazine chemistry is well-known and offers
many advantages (the use of strong acid catalysts is avoided
and polymerization is accomplished by ring-opening reac-
tion without by-product formation), only recently polyben-
zoxazines with enhanced structural properties have been
successfully synthesized, alone [8–11] or formulated with
suitable additives [12–14].
Monomeric benzoxazine compounds are bicyclic het-
erocycles extensively studied since the early 1940s and gen-
erated by the Mannich-like condensation of a phenol
derivative, formaldehyde (or its analogues), and a primary
amine by employing either solution or solventless methods.
Various phenols and amines with different substituted
groups could be used as starting materials for the benzox-
azine synthesis offering tremendous molecular design
flexibility into the benzoxazine chemistry to tailor the
Handbook of Benzoxazine Resins. DOI: 10.1016/B978-0-444-53790-4.00064-3
# 2011 Elsevier B.V. All rights reserved.
molecular structure and thus the resin properties for specific
applications. Most of the benzoxazine resins available
today derive from difunctional phenols. However, the
resulting difunctional benzoxazines are solid or high
viscosity products at room temperature, which makes their
processing difficult, requiring high temperature and pres-
sure conditions. Moreover, they are usually brittle materials
in the cured state. The objective of this work was, therefore,
the development of benzoxazine resins with improved
processing and handling characteristics in order to over-
come the shortcomings of the conventional benzoxazines.
We have recently focused our attention on the synthesis
of new low viscosity cardanol-based benzoxazines, as pos-
sible alternatives to the standard petroleum-based ones [15].
Cardanol is an industrial oily alkyl-phenolic product
obtained by the vacuum distillation of “cashew nut shell liq-
uid” (CNSL), a renewable natural resource obtained from
the cashew (Anacardium occidentale L.) nut as a by-prod-
uct during the process of removing the cashew kernel from
the nut [16–21]. The literature reports only few examples of
cardanol-based benzoxazines and their potential applica-
tions. They were studied as a matrix for natural fiber-rein-
forced composites [22] and as reactive diluents in the
synthesis process of bisphenol A benzoxazines [23].
In this work, a monofunctional liquid cardanol-based
benzoxazine (named CA-a; Figure 1), was prepared and
used as a reactive diluent and toughening agent for a
bisphenol A-based benzoxazine (named BA-a).
In particular, different mixtures of CA-a and BA-a were
prepared and studied in order to assess the influence of the
cardanol-based benzoxazine on the rheological, thermal,
viscoelastic, and mechanical properties of the bisphenol
A based one.
365
366 PART V
R:
O N
2. EXPERIMENTAL
2.1. Materials
Cardanol (with a purity of about 95%) was obtained by thin
film distillation of CNSL (using a vacuum of about 1 torr,
a preheating column at about 220
C, a feed-rate of 700 Kg/h,
and a distillation temperature of 240
C). BA-a was prepared
as previously reported [11] using bisphenol A (97%) pro-
vided from Sigma-Aldrich (Steinheim, Germany). Parafor-
maldehyde (95%), aniline (99%), analytical grade diethyl
ether, and deuterated chloroform (CDCl3, 99.8 atom% D)
were purchased from Sigma-Aldrich (Steinheim, Germany)
and used as received without further purification.
2.2. Measurements
2.2.1. Fourier Transform Infrared (FT-IR)
Spectroscopic Analysis
FT-IR spectra were recorded on a Perkin-Elmer Spectrum
One FT-IR spectrophotometer by using a KBr disk in the
spectral range from 4000 to 400 cm1.
2.2.2. Nuclear Magnetic Resonance (NMR)
Spectroscopic Analysis
Proton nuclear magnetic resonance (1H-NMR) spectra were
recorded on a Varian 500 NMR spectrometer operating at
500 MHz with CDCl3 as solvent. Sample temperature
was stabilized at 25
C.
2.2.3. Rheological Analysis
Isothermal rheological experiments were carried out using a
parallel plate rheometer (ARES, Rheometrics Scientific) at
100
C (below the melting point temperature of the BA-a).
The rheological analyses were performed in steady shear
mode at shear rates ranging from 0.1 to 100 s1.
2.2.4. Differential Scanning Calorimeter (DSC)
Analysis
DSC analyses were carried out by using a Mettler Toledo
DSC 823e. All samples were prepared in sealed aluminum
pans and the nonisothermal scans were performed at 10


C/min in a temperature range of 25-300
C under nitrogen
Renewable Resources-Based Polybenzoxazine Materials
FIGURE 1 Chemical structure of the benzoxazine CA-a.
atmosphere (80 mL/min). Small sample amounts (3-5 mg)
were tested in order to obtain isothermal conditions.
2.2.5. Dynamic Mechanical Thermal Analysis
(DMTA)
DMTA were carried out by using a Rheometrics Scientific
DMTA ARES Model equipped with a 200- to 2000-g/cm
dual range force rebalance transducer. Temperature sweep
experiments were performed at temperatures from 25 to at
least 50
C higher than the glass transition temperature of
each sample, using a heating rate of 5
C/min, a frequency
of 1 Hz, and applying to the samples a sinusoidal strain with
amplitude of 0.1%. The tests were carried out in torsion
mode on prismatic bars of rectangular cross-section using
specimens with dimensions of 40 mm  10 mm  1.2 mm.
2.2.6. Thermogravimetric Analysis (TGA)
Thermogravimetric investigations were performed on a
Mettler Toledo TGA/STDA 851e. The samples (15-20 mg)
were heated from 25 to 850
C at a heating rate of 10
C/min
under a dry air flow (balance purge, 150 mL/min; sample
purge, 80 mL/min).
2.2.7. Flexural Test
Mechanical flexural properties of the samples cured were
investigated according to the ASTM 790, using a dyna-
mometer LLOYD LR 30 K equipped with a 5-kN capacity
load cell. A three-point bending test was carried out until the
specimen broke occurred at a testing speed of 1.3 mm/min,
using a support span of 50 mm. Five specimens of
80 mm  12.7 mm  3.2 mm were tested for each sample
at room temperature.
2.2.8. Impact Test
The Izod pendulum impact resistance of the samples was
investigated according to the ASTM D 256. The reversed
notch Izod test method E was applied. A standardized
ATS FAAR IMPats-15 machine, equipped with a 5500-J
hammer, was used to perform the tests. The testing machine
provided also the automatic evaluation of the windage and
friction correction to be applied to each measurement. The
test results are the average of five trials.
Chapter 19 Study of a Cardanol-Based Benzoxazine as Reactive Diluent
3. RESULTS AND DISCUSSION
3.1. Synthesis of the CA-a Benzoxazine
In a 100-mL 3-necked round bottom flask, equipped with a
thermometer and a Dean-Stark apparatus connected to a
condenser, cardanol (10 g, 0.033 mol) was preheated at
60
C and aniline (3.6 mL, 0.033 mol) was then charged.
Paraformaldehyde (2.07 g, 0.065 mol) was then added,
keeping the temperature around 85
C. The system was
stirred for 4 h (following the reaction by TLC), then the
temperature was raised to 120
C to remove the water gen-
erated from the condensation reaction. The benzoxazine
thus obtained was recovered as an amber liquid (yield
91%) and used without any further purification.
3.2. Characterization of the CA-a
Benzoxazine
The FT-IR spectrum of CA-a, reported in Figure 2, shows
the characteristic absorption bands of the benzoxazine due
to the asymmetric and symmetric stretching of ArOC
group at 1241 and 1031 cm1, respectively. The absorption
bands due to C H (3009-2854 cm1) and C¼¼C (1579-
1
1622 cm ) groups can be also observed. The band due
to the phenolic OH of cardanol at about 3344 cm1 is
absent, suggesting a complete conversion of the hydroxyl
group of cardanol to oxazine ring. The absence of the char-
acteristic absorption bands of aniline due to the asymmetric
and symmetric NH stretching (3442 and 3360 cm1,
respectively), NH bending (1619 cm1), and CN
FIGURE 2 FT-IR spectrum of the benzoxazine CA-a.
Transmittance (%)
367
stretching (1281 cm1) confirm the absence of unreacted
aniline in the CA-a monomer and, therefore, the complete
condensation reaction.
The 1H-NMR spectrum of CA-a also confirmed the
benzoxazine structure, showing the following typical sig-
nals: d 7.4 (m, Ar); 6.93 (d, Ar, J ¼ 7.4 Hz); 6.81 (d, Ar,
J ¼ 7.1 Hz); 6.77 (s, Ar); 5.85 (m, CH¼¼CH2); 5.45
(m, CH¼¼CH); 5.37 (s, 2H, OCH2N); 5.17 (dd,
CH¼¼CH2); 4.57 (s, ArCH2N); 2.91 (aliphatic CH2
protons); 2.64 (t, CH2Ar); 2.18-2.02 (aliphatic CH2 pro-
tons); 1.63 (m, CH2); 1.40-1.22 (m, CH2); 0.94 (t, 3CH3).
In particular, the presence of the typical singlets cen-
tered at about 5.4 and 4.6 ppm, due to the hydrogen atoms
of the two methylene groups bonded to the nitrogen atom,
was consistent with the proposed benzoxazine structure.
3.3. Processing Method
In the present work, the following samples of different com-
position were studied: the pure BA-a, the pure CA-a, and
mixtures of the two benzoxazines containing 10%, 20%,
and 30% by weight of CA-a. The abbreviations used
hereafter for the samples studied are reported in Table 1.
The mixtures were prepared dissolving BA-a and CA-a in
diethyl ether under stirring at 70
C for 1 h. Then the solvent
was removed by heating under vacuum at 80
C for 20
minutes. The pure BA-a and CA-a samples were analyzed
without any treatment. All samples were thermally cured into
a closed mold at 150
C for 1 h, then at 220
C for 1 h, and
finally at 240
C for 1 h, applying a pressure of 0.1 MPa.
140
120
100
80
60
40
20
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm –1)
368 PART V Renewable Resources-Based Polybenzoxazine Materials

TABLE 1 Sample Compositions and Corresponding Abbreviations

Benzoxazine from Bisphenol A (%w) Benzoxazine from Cardanol (%w)

BA-a 100 0
CA-a 10 90 10
CA-a 20 80 20
CA-a 30 30 30

CA-a 0 100

30,000

25,000
25,000
Viscosity @ 100 ºC (cPs)

20,000

15,000

10,000

5000
5000
3450
2500

5.5
0
0 10 20 30 100
Ca-a (%)W
FIGURE 3 Viscosity versus CA-a amount at 100
C.

3.4. Rheological Measurements
The results of the viscosity measurements performed on the
samples listed in Table 1 are reported in Figure 3. All sam-
ples showed a Newtonian behavior. As can be observed, the
addition of CA-a produced a progressive reduction of the
viscosity value, as expected considering that the BA-a
and CA-a benzoxazines are solid and liquid compounds
at room temperature, respectively.
3.5. DSC Analysis
DSC studies were performed in order to investigate the
polymerization behavior of the samples reported in
Table 1. Nonisothermal DSC tests were carried out on
the uncured samples. A weight loss lower than 5% was
measured for all samples analyzed, indicating a low volatile
release during the cure process. The samples appeared solid
at room temperature after the nonisothermal tests. Figure 4
shows the DSC thermograms of the samples analyzed. The
corresponding DSC data are summarized in Table 2.
As shown in Figure 4, a single exothermic peak was
observed for the pure BA-a and CA-a samples, due to the
opening of the benzoxazine ring and the next polymeriza-
tion reaction [23,24].
An onset temperature of polymerization (To) of 142.0
C
and an exotherm peak temperature (Tp) of 220.0
C were
measured for the BA-a; the higher values (234.5 and
263.0
C, respectively) found for the pure CA-a could be
attributed to the steric hindrance of the CA-a molecule,
due to the presence of the long alkenyl side chain of the car-
danol moiety. Moreover, as reported in Table 2, the
Chapter 19 Study of a Cardanol-Based Benzoxazine as Reactive Diluent 369

FIGURE 4 DSC thermogram of BA-a (-□-), CA-a 1.0

(-þ-), CA-a 10 (-○-), CA-a 20 (-x-), and CA-a 30 (-D-).
0.8

0.6

0.4

Heat flow (W/g)

0.2

0.0

–0.2

–0.4

–0.6

–0.8
100 150 200 250 300
Temperature (°C)

TABLE 2 Results of the DSC Analysis of the Benzoxazine Resins

To (
C) Tp (
C) △H (J/g)
BA-a 142.0 220.0 360.0

CA-a 10 135.0 219.0 315.0

CA-a 20 134.0 218.0 283.5
CA-a 30 135.0 219.0 265.0
CA-a 234.5 263.0 74.0

polymerization enthalpy per unit mass of the pure CA-a is
much lower than that measured for the pure BA-a. This
behavior could be explained considering that the overall num-
ber of functionality per unit mass decreases with the amount of
CA-a, with CA-a and BA-a being a monofunctional and a
difunctional monomer, respectively. In addition, the steric
effect due to the long alkenyl chain of the CA-a could have
a negative influence on the cross-link density of the resins.
A single exothermic peak was also observed for the ben-
zoxazine mixtures, suggesting a copolymerization mecha-
nism between the two benzoxazines. As can be seen in
Table 2, no significant change of To and of Tp was observed
varying the amount of CA-a in the benzoxazine mixtures
when compared to the corresponding values recorded for
the pure BA-a. Moreover, a decrease of the reaction
enthalpy per unit mass was observed increasing the amount
of CA-a, as expected considering the contribution of both
BA-a and CA-a to the reaction enthalpy.
3.6. Dynamic Mechanical Thermal Analysis
DMTA experiments were performed in order to study the
viscoelastic properties of the benzoxazine resins and to eval-
uate their Tg. The samples were prepared and polymerized
as described above. The evolution of the storage modulus
(G0 ) and loss modulus (G00 ) as a function of the temperature
was recorded in each experiment. The storage and loss
modulus curves obtained for the samples are reported in
Figures 5 and 6, respectively, for comparison purposes.
As shown in Figure 5, it is possible to identify for all
samples analyzed three regions in the G0 evolution related
to the glassy, viscoelastic, and rubbery states, respectively.
In Figure 7, the G0 values, measured at room tempera-
ture, were plotted as a function of the mixture composition;
as can be seen, the G0 modulus decreases as the CA-a
content increases in the samples. This behavior can be
explained considering that the G0 module provides
370 PART V Renewable Resources-Based Polybenzoxazine Materials

FIGURE 5 Evolution of the storage modulus G0 of BA-a

(-□-), CA-a 10 (-○-), CA-a 20 (-x-), and CA-a 30 (-D-).

1E9
Storage modulus G' (Pa)

1E8

50 100 150 200 250 300

Temperature (°C)

2.00E + 008
Loss modulus G⬙ (Pa)

1.50E + 008

1.00E + 008

5.00E + 007

0.00E + 000
60 120 180 240 300
Temperature (°C)
FIGURE 6 Evolution of the loss modulus G00 of BA-a (-□-), CA-a 10 (-○-), CA-a 20 (-x-), and CA-a 30 (-D-).

information about the capacity of a material to store elastic
energy under small torsion deformations. The elastic energy
stored increases with the resistance to the motion of the lit-
tle molecular segments between two cross-link points.
Since CA-a is a monofunctional monomer, its blend with
BA-a leads to a decrease of the cross-link density of the
final polymer, resulting in a decreased resistance to the
movement of the molecular segments. The steric hindrance
due to the long alkyl side chain of the cardanol moiety in the
CA-a must be also considered because it has a negative
effect on the cross-link density of the resins. In addition,
since the alkyl chain of the cardanol acts as intramolecular
plasticizer, it increases the flexibility of molecular
segments.
The loss modulus measured is related to the energy dis-
sipated as heat under small torsion deformations. Therefore,
in this work we have assumed as Tg the temperature corre-
sponding to the maximum value of G00 . As can be seen in
Figure 6, the DMTA analysis showed only one asymmetri-
cal peak in the G00 modulus for all mixtures analyzed,
Chapter 19 Study of a Cardanol-Based Benzoxazine as Reactive Diluent 371

FIGURE 7 Storage modulus G0 versus the composition of the

benzoxazine resins.
1.80E + 009

Storage modulus (Pa)

1.60E + 009

1.40E + 009

0 5 10 15 20 25 30
Composition (%w CA-a)

FIGURE 8 Glass transition temperature versus the composi-

tion of the benzoxazine resins. 160
Glass transition temperature (°C)

150

140

130

120

110
0 5 10 15 20 25 30
Composition (%w CA-a)

supporting the previous hypothesis that the two benzox- (1) An increase in G00 value in the glassy state;
azines BA-a and CA-a copolymerize without any apprecia- (2) An increase in the G00 peak height at the glass
ble phase separation. transition.
Figure 8 shows the Tgs of the resins as a function of the
The experimental data show a decrease in the G00 peak
mixture composition: the Tg decreases with the increase of
height at the glass transition and an increase in the G00 value
the CA-a content, as expected considering the remarks
in the glassy state, as the CA-a content becomes higher
reported above about the evolution of G0 varying the sample
inside the mixture.
composition.
This behavior may be explained considering that in the
The height and width at half-height of the loss modulus
glassy state only the vibrational motions of single atoms or
peak were also measured in order to get information about
groups of few atoms are allowed, while at the glass transition
the mobility of molecular segments and the polymer
rotational motions of polymer molecule segments occur. In
network homogeneity when the composition of the resin
light of this, the cardanol long alkyd side chain can largely
analyzed varies. The data obtained are listed in Table 3.
affect the mechanical properties in the viscoelastic rather
The increase in the CA-a in the benzoxazine network
than in the glassy region. At the glass transition, the cardanol
results in an improvement of the molecular mobility.
chains are free to make long-range motions, hindering, by
Two phenomena would be therefore expected, considering
physical entanglements, the movements of neighboring
that G00 is related to the viscous losses:
372 PART V Renewable Resources-Based Polybenzoxazine Materials

TABLE 3 Dynamic Mechanical Data Related to the Loss Modulus Peak

Sample Position (
C) Height (Pa) Width at Half Height (
C)

BA-a 161.0 1.3E þ 8 25.2
CA-a 10 156.0 8.6E þ 7 33.3
CA-a 20 124.0 6.4E þ 7 35.1
CA-a 30 112.0 3.4E þ 7 36.1

FIGURE 9 TGA thermogram and its derivative for

100 0.040 BA-a benzoxazine.
90
0.035
80

Rate of weight loss (%/min)

0.030
70
Weight loss (%)

60 0.025

50 0.020
40
0.015
30
0.010
20

10 0.005

0 0.000
100 200 300 400 500 600 700 800
Temperature (°C)

molecules. This can be the explanation why the damping
peak becomes lower, increasing the CA-a benzoxazine.
The physical contribution described above is negligible in
the glassy region where the cardanol chains are in a frozen
state, and the mechanical behavior is determined mainly
by the benzoxazine network degree of cross-link, which be-
comes lower as the CA-a content increases.
Moreover, a broadening of the G00 peak can be observed
as the CA-a content increases in the benzoxazine resins, as
evidenced by the width at half-height values reported in
Table 3.
In conclusion, the presence of CA-a increases the
molecular structure distribution inside the mixtures studied.
The behavior observed can be explained considering that
the CA-a can copolymerize with BA-a in different ways
with the possibility to generate also branched structures
of different molecular weight.
3.7. Thermogravimetric Analysis
Thermogravimetric studies were performed in order to
investigate the thermal stability of the cured samples.
In Figures 9 and 10 are reported the TGA thermograms
and their derivatives for the pure BA-a and CA-a benzox-
azines, respectively.
The decomposition temperatures for the 5%w (T5%) and
10%w (T10%) mass loss as well as the mass loss values at
600
C and at 700
C are reported in Table 4.
As shown in Figures 9 and 10, for both benzoxazines it is
possible to identify a three-stage weight loss process. Max-
imum weight loss rates of 3.88% min1 at 392
C and
12.95% min1 at 448
C were measured for BA-a and
CA-a benzoxazines, respectively.
The thermal patterns measured for BA-a benzoxazine
are in accordance with those reported in the literature [25].
As previously reported for the pure BA-a [25,26], the
weight loss observed could be attributed to the degradation
of the phenolic linkages and of the Mannich bridges in the
benzoxazine polymer. In addition, for the CA-a benzox-
azines, the degradation of the double bond a-carbon and
of the methylene linkages in the alkyl side chain of the car-
danol moiety occur at temperatures above 200
C [27] and
in the temperature range of 440-500
C, respectively [28].
As reported in Table 4, the T10% values found for BA-a
and CA-a are comparable, while the T5% value of CA-a is
Chapter 19 Study of a Cardanol-Based Benzoxazine as Reactive Diluent 373

FIGURE 10 TGA thermogram and its derivative for

100 0.14
CA-a benzoxazine.
90
0.12

Rate of weight loss (% /min)

80

70 0.10

Weight loss (%)

60
0.08
50

40 0.06

30 0.04
20
0.02
10

0 0.00
100 200 300 400 500 600 700 800
Temperature (°C)

TABLE 4 Thermal Degradation Data of the Benzoxazine Resins

Sample T5% (
C) T10% (
C) Mass Loss at 600
C (%) Mass Loss at 700
C (%)
BA-a 333.0 347.5 71.5 74.0
CA-a 10 312.0 353.0 65.0 90.0

CA-a 20 325.0 372.0 68.0 92.0

CA-a 30 332.0 380.0 69.0 93.5
CA-a 299.0 345.0 82.0 97.0

slightly lower than that recorded for the BA-a. Moreover,
the pure CA-a exhibits higher weight losses than the pure
BA-a at both 600 and 700
C.
The TGA curves obtained for the benzoxazine mixtures
are shown in Figure 11 and compared with those of the pure
benzoxazines. As can be seen, the general thermal degrada-
tion patterns of all mixtures are very similar.
As can be seen in Table 4, the thermal behavior of the
mixtures varies with the content of CA-a. In particular,
an increase in the T5% and T10% values can be observed
as the CA-a amount increases. Moreover, the T10% values
recorded for all mixtures are higher than that found for
the pure BA-a. In addition, a better thermal behavior was
observed at 600
C for all mixtures if compared to that of
the pure BA-a, as indicated by the corresponding mass loss
values reported in Table 4. On the other hand, an increase of
the mass loss values at 700
C was observed for all mixtures
as regards the pure BA-a, indicating that the thermal stabil-
ity at this temperature is worsened by the increase of the
CA-a content in the mixtures.
The results obtained demonstrate that the presence of
the monofunctional CA-a benzoxazine improves the
thermal stability of the resins in the temperature range of
350-600
C while it leads to detrimental effects at temper-
atures above 600
C.
3.8. Mechanical Properties
The effects of the presence and content of CA-a on the flex-
ural and impact mechanical properties of the benzoxazine
resins analyzed were evaluated and the data obtained are
reported in Table 5. For all samples tested, the fracture
was found to be brittle.
The CA-a benzoxazine resin shows higher values of both
elongation at break and Izod impact strength when compared
to the BA-a resin. Moreover, the values of those properties
increase with the CA-a content in the benzoxazine mixtures.
On the other hand, the presence of CA-a reduces both the
flexural strength and flexural modulus of the benzoxazine
resins and the higher the amount of CA-a was used, the lower
flexural strength and modulus were obtained.
This behavior can be explained considering the negative
influence of the CA-a chemical structure on the cross-link
density of the benzoxazine resins.
374 PART V Renewable Resources-Based Polybenzoxazine Materials

FIGURE 11 Thermogravimetric curves of the

100 following benzoxazine resins: (BA-a) (-□-), (CA-a)
þ-), and (CA-a
(-○-), (CA-a 10) (-þ-), (CA-a 20) (-
90
30) (-D-).
80

70
Mass loss (%)

60

50

40

30

20

10

0
50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850
Temperature (°C)

TABLE 5 Mechanical Properties of the Benzoxazine Resins

Sample Flexural Strength (MPa) Flexural Modulus (GPa) Strain at Break (%) Izod Impact Strength (J/m2)
BA-a 139.0  12.0 5.1  0.2 3.1  0.1 3122.0  288.0

CA-a 10 125.0  14.0 4.4  0.4 3.2  0.3 6300.0  180.0

CA-a 20 105.0  6.1 3.4  0.1 3.5  0.2 7800.0  345.0
CA-a 30 93.0  3.4 2.7  0.2 4.2  0.3 8800.0  412.0

The Izod tests bear evidence of an increasing toughness
of the specimen as the relative amount of CA-a increases.
The results obtained can be explained considering that
the alkyl chain of cardanol hinders the reciprocal move-
ments of the broken macromolecules while the crack
spreads throughout the specimen width.
4. CONCLUSION
In this work, the thermal, viscoelastic, and mechanical
properties of benzoxazine resins obtained from the mixture
of a low viscosity CA-a and the BA-a were studied. Three
different mixtures of BA-a and CA-a, containing 10%,
20%, and 30% by weight of CA-a, were prepared and stud-
ied to illustrate how different amounts of the cardanol
derivative affect the properties of the final benzoxazine
resins.
Rheological studies performed at 100
C on the benzox-
azine mixtures revealed that the use of CA-a reduces the
viscosity of the reactive mixture, making it suitable as a
reactive diluent. The results obtained from the nonisother-
mal DSC analysis suggested a copolymerization reaction
between the two benzoxazines BA-a and CA-a, occurring
in a temperature range similar to that shown by the BA-a
resin. The DMTA results gave us information about both
their transition temperature and segmental molecular
mobility. A single-glass transition temperature signal was
recorded for each mixture composition analyzed, confirm-
ing the copolymerization hypothesis. Moreover, lowering
of the Tgs was verified as the amount of the CA-a increased
because of the reduction of the cross-linking density. Two
elements contributed to those results: the steric hindrance of
the alkyl side chain of the cardanol moiety in the CA-a and
the lower functionality of CA-a with respect to BA-a.
In addition, the TGA analysis demonstrated that the pres-
ence of the monofunctional CA-a benzoxazine improves
the thermal stability of the resins in the temperature range
of 350-600
C while it leads to detrimental effects at tem-
peratures above 600
C. The thermal behavior for the com-
positions containing the cardanol-based benzoxazine is
rather unexpected. In fact, the cardanol-based benzoxazine
introduces thermally less stable aliphatic chains into the
reactive mixture and in addition reduces the cross-link den-
sity of the final benzoxazine polymer. The TGA is not
Chapter 19 Study of a Cardanol-Based Benzoxazine as Reactive Diluent
sufficient to clarify the thermal phenomena observed. Fur-
ther analyses are necessary and they will be carried out in a
future work.
Finally, the mechanical test data revealed that CA-a
improves the toughness of the resins thanks to the presence
of the long alkyl chain of the cardanol moiety. Therefore,
relatively low amounts of CA-a allow improvement of
the toughness, the processability, and the thermal resistance
of conventional benzoxazines with slight detrimental
effects over thermal and mechanical properties.
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