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Synthesis and Copolymerization of Fully Biobased Benzoxazines from

Renewable Resources

Article in ACS Sustainable Chemistry & Engineering · October 2014

DOI: 10.1021/sc500548c

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pubs.acs.org/journal/ascecg

Synthesis and Copolymerization of Fully Biobased Benzoxazines

from Renewable Resources
P. Thirukumaran, A. Shakila Parveen, and M. Sarojadevi*
Department of Chemistry, Anna University, Chennai 600025, Tamilnadu, India

ABSTRACT: A solventless method was adopted to synthesize

two benzoxazine monomers from naturally occurring sources,
i.e., eugenol (an extraction from clove), furfurylamine, stea-
rylamine, and paraformaldehyde. The structure of the ex-
tracted eugenol and synthesized monomers were supported by
FT-IR, 1H NMR, 13C NMR, and mass spectral analysis. The
monomers were polymerized/copolymerized via ring-opening
polymerization by heating as shown by FT-IR (disappearance
of the peak due to oxazine ring at 920 cm−1) and differential
scanning colorimetry (DSC). The exothermic peak associated
with curing was observed between 198−254 °C. DSC analysis
shows that the onset of curing temperature for the copolymers
decreased linearly from 207−202 °C on increasing the content of F-Bz. The results from TGA analysis indicate that PF-Bz shows
the maximum thermal stability when compared with PS-Bz and their copolymers. In the case of the copolymers, as the F-Bz
content is increased, the thermal stability also increases. All the polymers also exhibit good flame retardant properties as shown
by their LOI values (more than 26).
KEYWORDS: Eugenol, Biobased benzoxazines, Solventless method, Cross-link density, Flame retardancy

■ INTRODUCTION
Benzoxazine is a newly developed thermosetting phenolic resin,
using alternative sustainable processes deserves the increasing
attention of both academic and industrial research.10,11
and it can be synthesized via Mannich condensation from In this study, eugenol, furfurylamine, stearylamine, and
phenol, amine, and formaldehyde.1,2 Benzoxazine has a single paraformaldehyde were chosen as raw materials (from natural
benzene ring fused to another six-membered heterocycle con- source) to synthesize polybenzoxazines and its copolymers.
taining one oxygen atom and one nitrogen atom. There are a Eugenol is a member of the phenyl propanoids class of chem-
number of possible isomeric benzoxazines, depending on the ical compounds. The name is derived from the scientific name
relative position of the two hetero atoms of the oxazine ring for clove, Eugenia aromaticum or Eugenia caryophyllate. Clove
system. Benzoxazine monomers can be polymerized by a ther- is commercially cultivated in India, Madagascar, Srilanka,
mally activated ring-opening polymerization reaction with no Indonesia, and South China. Eugenol is responsible for the
reaction by-products released and no catalyst required.3,4 aroma of cloves. It is the main component in the essential oil
During the self-cross-linking polymerization reaction, the extracted from cloves comprising 72−90% of the total. It is a
Mannich bridge structure −CH2−NR−CH2 was formed clear to pale yellow oily liquid extracted from certain essential
between benzoxazine molecules through the ring-opening reac- oils especially from clove, nutmeg, cinnamon, basil, and bay
tion of the oxazine ring.5−7 So, as the polymerization proceeds, leaf. It is slightly soluble in water and soluble in organic sol-
benzoxazine gradually gets converted into a three-dimensional vents. It has a spicy clove-like aroma. Clove oil is widely used
network of polybenzoxazine. The benxoxazine-based materials for flavoring pastry, special sauces, and condiments. It is also
possess excellent mechanical and thermal properties (350− used in medicines, especially in preparations for the gums and
400 °C), high dimensional stability, low water absorption, high teeth.12−14 Furfurylamine is a colorless to yellow liquid with an
char yield (28−66%), and near zero shrinkage upon curing, ammonia odor. It is an intermediate in the synthesis of many
which make them a promising matrix candidate for high-perfor- pharmaceutical, agricultural, and industrial chemicals. It is
mance composites especially in the microelectronics, aerospace, derived from corncorbs and wheat bran, which are agricultural
and packaging industries.8 The main strategies for tailoring the byproducts. Stearylamine is obtained from vegetable oils. Para-
molecular structures of polybenzoxazine can be classified into formaldehyde is the smallest polyoxymethylene, which is the
three groups: (i) modification of benzoxazine monomers with polymerization product of formaldehyde with a typical degree
additional functionalities, (ii) incorporation of benzoxazine
moieties into polymer chains, and (iii) copolymerization of two Received: August 25, 2014
or more benzoxazine monomers.9 Nowadays, the development Revised: October 28, 2014
of a biobased polymer (based on renewable organic raw materials)

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ACS Sustainable Chemistry & Engineering Research Article

Scheme 1. Synthesis of Benzoxazine Monomers

Figure 1. FT-IR spectrum of eugenol.

and below the transition region of the second scan curve is defined as
Tg. Thermogravimetric analysis (TGA) was performed using a TA Q
600 thermal analyzer. Cured samples were analyzed in an open silicon
Table 1. DSC Data of F-Bz, S-Bz, and Their Copolymers pan at a heating rate of 20 °C/min in a nitrogen atmosphere, up to a
maximum temperature of 800 °C.
sample mole ratio Tm Tonset Tmax Tprocessing window Extraction of Eugenol. Fifteen grams of cloves was taken and
no. sample S-Bz/F-Bz (°C) (°C) (°C) (°C) crushed well. It was then transferred into a 250 mL round-bottomed
1 a 1:0 49 218 231 169 flask and to it distilled water (150 mL) was added, and the contents
were heated to 50 °C. When the solution begins to boil, the condensed
2 b 3:1 49, 74 207 246 133
vapor was collected as a milky white distillate in an Erlenmeyer flask.
3 c 1:1 49, 74 204 243 130
The distillation process was continued until no more oily material was
4 d 1:3 49, 74 202 226 128 seen in the condenser. The distillate was transferred into a 250 mL
5 e 0:1 74 198 222 124 separatory funnel and to it 25 mL of dichloromethane was added. Two
layers were formed, which were separated. To the organic layer, a 5%
solution of KOH was added, and the aqueous layer was separated. The
of polymerization of 8−100 units. Paraformaldehyde com- process was repeated twice, and the combined aqueous layer was
monly has a slight odor of formaldehyde due to decomposition. acidified by using 5% HCl dropwise until the solution turned cloudy.
The extraction of eugenol, synthesis of benzoxazine mono- To the cloudy solution, dichloromethane was added, from which the
mers, and copolymerization, along with the characterization, organic layer was separated. The organic layer (dichloromethane layer)
thermal polymerization, and thermo-mechanical properties of was further washed with distilled water, and the separated organic layer
these new benzoxazines are described. The curing behavior of was washed with 15 mL of saturated sodium chloride solution. The
the individual benzoxazine monomers (F-Bz and S-Bz) and organic layer thus obtained was dried with anhydrous sodium sulfate.
their effect on copolymerization has been investigated. The dichloromethane solution was further distilled to get a pale yellow

■
viscous liquid of eugenol.15,16 Yield: 65%. FT-IR (KBr, cm−1): 3521,
3078, 3009, 2970, 2939, 2901, 2839, 1643, 1612, 1512, 1458, 1435,
EXPERIMENTAL SECTION 1366, 1273, 1237, 1149, 1120, 1034, 995, 910, 849, 818, 749, 648,
Materials. Stearylamine was purchased from Sisco Research 549, 555. 1H NMR (CDCl3, ppm): 3.31 (d, 2H), 3.82 (s, 3H), 5.08
Laboratories, Pvt. Ltd., India. Furfurylamine was purchased from (d, 2H), 5.66 (s, 1H), 5.95 (m, 1H), 6.5−7.0 (m, 3H). 13C NMR
Aldrich, India. Paraformaldehyde was purchased from Merck Limited, (CDCl3, ppm): 40, 56, 110, 114, 115, 121, 132, 137, 144, 146;
India. Dichloromethane (DCM) was purchased from Alfa Aesar m/e value, 163.0
(Johnson Mathew Company), India, Pvt. Ltd. Tetrahydrofuran (THF) Synthesis of 6-Allyl-3-furfuryl-8-methoxy-3,4-dihydro-2H-1,3-
was purchased from Fisher Scientific (a part of Thermo Fisher benzoxazine [F-Bz]. Eugenol (0.05 mol, 8.2 g), furfurylamine (0.05
Scientific, India, Pvt. Ltd.). All other chemicals are of analytical grade mol, 4.85 g), and paraformaldehyde (0.1 mol, 3 g) were mixed and
and were purchased from Spectrochem Pvt. Ltd., India. All chemicals stirred at room temperature until the solid was dissolved. After which
were used without further purification. the mixture was heated to 100 °C for 2 h, cooled to room temperature,
Instrumention. Fourier transform infrared (FT-IR) spectra of the and concentrated under reduced pressure. The residual solid was
samples were obtained using an ABB Bomem (Model MB 3000) crystallized from ethanol at 70 °C, filtered, and dried under vacuum to
spectrometer. The samples were ground with spectroscopy-grade KBr obtain F-Bz as a pale yellow powder. Yield: 91%, mp, 74 °C. FT-IR
and made into pellets. 1H (500 MHz) and 13C (125 MHz) nuclear (KBr, cm−1): 2908, 2839, 1589, 1497, 1458, 1296, 1227, 1149, 1011,
magnetic resonance (NMR) spectra were recorded on a Joel spec- 920, 833, 733. 1H NMR (CDCl3, ppm): 3.21 (d, 2H), 3.80 (s, 3H),
trometer with tetramethylsilane (TMS) as the internal standard. Solu- 3.85 (s, 2H), 3.97 (s, 2H), 4.88 (s, 2H), 5.03 (d, 2h), 5.87 (m, 1H),
tions were prepared in CDCl3. Differential scanning calorimetry 6.25−6.84 (m, 4H), 7.29 (d, 1H). 13C NMR (CDCl3, ppm): 39, 47,
(DSC) was performed in a TA Instruments Q10 model using 5−10 mg 48, 55, 81, 108, 109, 114, 115, 118, 120, 131, 136, 139, 141, 146, 152;
of the sample at a heating rate of 10 °C/min in a nitrogen atmosphere. m/e value, 285.80 (Scheme 1).
Dynamic mechanical analysis (DMA) was carried out using a Netzsch Synthesis of 6-Allyl-3-octadecyl-8-methoxy-3,4 dihydro-2H-1,3-
242 DMA at a heating rate of 10 °C/min from 30 to 250 °C. The glass benzoxazine [S-Bz]. Eugenol (0.05 mol, 8.2 g), stearylamine (0.05
transition temperature (Tg) values were obtained by second heating mol, 13.5 g), and paraformaldehyde (0.1 mol, 3 g) were mixed and
scans; the samples were heated from room temperature to 350 °C, stirred at room temperature until the solids were dissolved. The
cooled to room temperature, and heated again to 350 °C under a solution was then heated to 100 °C for 2 h, cooled to room tem-
nitrogen atmosphere. The heating rate of the second scans was perature, and concentrated under reduced pressure. The residual solid
10 °C/min. The halfway point between the two tangent lines above was crystallized from ethanol at 70 °C, filtered, and dried under

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Figure 2. 1H NMR spectrum of eugenol.

Figure 3. 13C NMR spectrum of eugenol.

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Figure 4. Mass spectrum of eugenol.

Figure 5. Gas chromatography of eugenol.

vacuum to obtain S-Bz as a pale yellow powder. Yield: 89%, mp 49 °C. and then post cured at 230 °C for 1 h. The cured samples were brown
FT-IR (KBr, cm−1): 2924, 2854, 1589, 1497, 1466, 1381, 1281, 1227, colored with 3 mm thickness. A similar procedure was adopted for the
1149, 1095, 995, 918, 841, 717. 1H NMR (CDCl3, ppm): 0.81 (t, 3H), other benzoxazine monomer (S-Bz) and their copolymers. The mole
1.18 (m, 30H), 1.47 (m, 2H), 2.69 (d, 2H), 3.22 (d, 2H), 3.76 (s, 3H), ratios of the copolymers are given in Table 1.

■
3.89 (s, 2H), 4.85 (s, 2H), 5.03 (d, 2H), 5.9 (m, 1H), 6.25−7.0 (m,
2H). 13C NMR (CDCl3, ppm): 15−35, 40, 50, 52, 56, 83, 110, 115, RESULTS AND DISCUSSION
118, 120, 131, 138, 142, 147; m/e value, 456.77 (Scheme 1).
Copolymerization of F-Bz and S-Bz. For the preparations of the Characterization of Extracted Eugenol. The chemical
F-Bz and S-Bz copolymers in a 1:3 mol ratio, 1 mol of the F-Bz structure of the extracted eugenol was confirmed by FT-IR,
1
monomer and 3 mol of the S-Bz momomer were taken and dissolved H NMR, and 13C NMR spectroscopy. Figure 1 shows the
in 10 mL of THF and stirred at room temperature until a homo- FT-IR spectrum of eugenol. The spectrum shows absorption
geneous solution forms. The solution was then transformed into a bands at 1034 and 1234 cm−1 due to symmetric and asym-
mold and cured in a heating oven at 100, 150, 200, and 230 °C each at metric stretching modes of C−O−C of the −OCH3 group
1 h to obtain the copolymer. In a similar way, the other copolymers attached to the benzene ring. A broad absorption at 3526 cm−1
were prepared by adding different mole ratios of the F-Bz and S-Bz
monomers. The copolymer mole ratios are given in Table 1.
shows the presence of the −OH group, whereas the alkyl group
Preparation of Samples for DMA Analysis. A synthesized benzo- present in eugenol gave symmetric and asymmetric stretch-
xazine monomer (F-Bz) (5 g) was dissolved in THF (10 mL) and ing vibrations at 2839 and 2939 cm−1. The bands at 1458
stirred for 30 min at room temperature and further stirred for 5 h in and 849 cm−1 correspond to the −CH in-plane and out-of-
open air to evaporate most of the THF. The solution was then poured plane bending modes of the trisubstituted benzene ring,
into the mold and cured at 100 °C/1 h, 150 °C/1 h, and 200 °C/1 h, respectively.17−19
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Figure 2 displays the 1H NMR spectrum of eugenol. The range of 6.5−7.0 ppm. The peak at 7.2 ppm is due to the
singlet at 3.82 ppm is due to the −OCH3 protons. The doublets solvent peak (CDCl3). Figure 3 shows the 13C NMR spectrum
at 3.21 and 5.05 ppm and the multiplet at 5.95 ppm are as- of eugenol. The methoxy carbons (−OCH3) gave peaks at
signed to the allyl protons [−CH2−CHCH2−]. −OH pro- 56 ppm. The alkyl carbons [−CH2−CHCH2] gave peaks at
tons appear at 5.66 ppm, and aromatic protons appear in the at 115, 137, and 40 ppm, and the aromatic carbons gave peaks
around 120−150 ppm.14,20,21
The mass spectrum of eugenol is shown in Figure 4, which
shows the molecular ion peak at 163 for eugenol, and the purity
of eugenol is confirmed by GC analysis as shown in Figure 5
showing 98.7% of eugenol.
Characterization of Synthesized Benzoxazine Mono-
mers. The structures of the benzoxazine monomers are
supported by the FT-IR spectra as shown in Figure 6. The
characteristic absorptions of the benzoxazine ring structure of
both F-Bz and S-Bz appeared at 1233 and 1029 cm−1 (due to
the asymmetric and symmetric stretching modes of C−O−C,
respectively), while the peak at 920 cm−1 confirms the presence
of a benzene ring with an oxazine ring attached to it.22 More-
over, the spectrum shows a peak at 1150 cm−1 for both of the
benzoxazines (F-Bz and S-Bz) due to the C−N−C symmetric
stretching vibrations. The asymmetric and symmetric stretching
vibration of methoxy carbonyl attached to the benzene ring was
Figure 6. FT-IR spectra of (a) F-Bz and (b) S-Bz benzoxazine found at 1227 and 1011 cm−1. Whereas both of the methylene
monomers. groups (−CH2), one in the benzoxazine ring and the other

Figure 7. 1H NMR spectra of (a) F-Bz and (b) S-Bz benzoxazine monomers.

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Figure 8. 13C NMR spectra of (a) F-Bz and (b) S-Bz benzoxazine monomers.

Figure 9. Mass spectrum of benzoxazine monomers (F-Bz).

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Figure 10. Mass spectrum of of benzoxazine monomers (S-Bz).

methylene protons (−CH2) connecting the furan and oxazine

ring resonate at 3.85 ppm. Similarly, the 1H NMR spectrum
(Figure 5) of S-Bz displayed two resonances centered at 3.89
and 4.85 ppm, which are consistent with the formation of the
oxazine ring, whereas the long aliphatic chain of the oxazine
gave multiplets at 2.69, 1.18, and 0.81 ppm.14,24 The peak at 7.2
ppm is due to the solvent peak (CDCl3).
The 13C NMR spectra shown in Figure 8 also confirm the
structures of F-Bz and S-Bz. The characteristic carbon reso-
nance of the oxazine ring is found at 48 and 81 ppm for Ph−
CH2−N and O−CH2−N, respectively. The peak at 55 ppm is
attribiuted to the −OCH3 carbon, and the peaks at 114, 136,
and 39 ppm are assinged to −CH2−CHCH− allyl carbons.
The furan ring carbons of F-Bz gave peaks between 100 and
150 ppm. The peak corresponding to the −CH2−N of the
furan ring appeared at 47 ppm, whereas the aliphatic moiety
attached to the oxazine ring of S-Bz gave characteristic peaks in
Figure 11. DSC curves of the F-Bz/S-Bz mixtures with various F-Bz between 15 and 35 ppm.14 The mass spectrum of F-Bz and
contents in molar ratios (a) 0%, (b) 25%, (c) 50%, (d) 75%, and S-Bz is shown in Figures 9 and 10, which shows the molecular
(e) 100%. ion peak at m/e = 285.80 for F-Bz and at m/e = 456.77 for S-Bz.
Thermal Behavior of Monomers and Polymers and
attached with the eugenol group, gave bands for its stretching Their Copolymers. The polymerization behaviors of the
vibrations between 2924 and 2854 cm−1, respectively.3,19,23 The individual monomers (F-Bz and S-Bz) and their copolymers
intensity of the C−H peaks (both symmetric and asymmetric) were studied using DSC at a heating rate of 10 °C/min under a
in S-Bz is more when compared with F-Bz, indicating the pre- nitrogen atmosphere from 30 to 350 °C. Figure 11 shows the
sence of an alkyl side chain of stearylamine. The peaks observed DSC thermograms of the monomers and their copolymers. The
at 1589, 995, and 733 cm−1 may be attributed to the vibrations data are summarized in Table 1. The two benzoxazine mono-
of the furan ring. mers (S-Bz and F-Bz) melt at 49 and 74 °C, which is shown by
The 1H NMR spectra shown in Figure 7 further confirms the sharp endotherms at this point. Similarly, when the two
structures of F-Bz and S-Bz. The resonance peaks at 3.97 and monomers are copolymerized, each copolymer displays two
4.88 ppm are assigned to Ph−CH2−N and −O−CH2−N of the endotherms corresponding to their individual melting points.
oxazine ring, respectively. The singlet at 3.8 ppm is due to the The onset of curing is around 218 °C for S-Bz and 198 °C for
−OCH3 protons. The doublets at 3.21, 5.87, and 5.03 ppm F-Bz. But for the copolymer mixtures, the onset of curing tem-
are assigned to [−CH2−CHCH2−] allyl protons. The furan perature decreased linearly with increasing F-Bz content
ring protons resonate at 6.25, 6.84, and 7.29 ppm, and the (from 207 to 202 °C). The presence of an electronegative atom
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Figure 12. FT-IR spectra of (a) F-Bz and (b) S-Bz at different curing temperatures.

Figure 13. FT-IR spectra of copolymers cured at different temperatures.

(i.e., oxygen) in the furan ring makes the attack of the furan 124 °C. Whereas for the copolymers, it is between 128 and
ring to the phenolic moiety of benzoxazine viable, thereby 133 °C, showing a wide range of processability for both the
promoting the curing reaction, thus confirming that copoly- monomers and their copolymers.24 In addition, the neat poly-
merization of F-Bz and S-Bz has occurred. The exothermic final mers and their copolymers showed another exothermic peak
for the individual monomers was observed at 234 and 249 °C, centered at 335 °C, which appears due to the degradation of
and for the copolymers, it was observed between 237 and the aliphatic chains present in it.25
257 °C. It is well known that ring-opening polymerization of The curing reaction of the monomers and copolymers were
benzoxazine will exhibit an exothermic peak around 200− further confirmed by FT-IR analysis. Figures 12 and 13 show
250 °C. The biobased benzoxazines (S-Bz and F-Bz) also the FT-IR spectra of the monomers and copolymers after
display a similar exothermic behavior in the high-temperature heating at 100, 150, 200, and 230 °C for 1 h at each tempera-
range. The processing window is defined as the temperature ture. The curing process proceeds via the cleavage of C−O−C
difference between the melting point and onset of polymer- bond of the oxazine ring. As a result, there is a decrease in the
ization. The S-Bz monomer shows a processing window of intensity of peaks around 920, 1029, 1233, and 1350 cm−1,
169 °C, and the F-Bz monomer shows a processing window of which is due to the stretching vibrations of the oxazine ring,
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Scheme 2. Copolymerization Mechanism of F-Bz/S-Bz Mixturesa

a
Illustration according to Wang et al.19

Figure 15. DSC curves (second scan) of F-Bz/S-Bz mixtures with

various F-Bz contents in molar ratios (a) 0%, (b) 25%, (c) 50%,
(d) 75%, and (e) 100%.

Figure 14. 1H NMR spectra of copolybenzoxazines (F-Bz/SBz molar O−CH2−N and at 4.0 and 3.95 ppm for the methylene protons
ratio 1:1) cured at different temperatures. of Ar−CH2−N. As shown in the figure, the oxazine ring
protons decreased on further curing at 150 and 200 °C. Finally,
C−O−C of the oxazine ring, and −CH2 of the benzene ring. At at 250 °C, a copolymer was formed that does not dissolve in
still higher temperatures (say 200 °C), the allyl group present the solvent and is shown by the absence of peaks. All these
in the eugenol part also involves in curing. This is supported by results confirm that copolymerization of the two benzoxazine
the disappearance of the stretching vibrations of the allylic monomers, F-Bz and S-Bz, has occurred.
moiety at 1636 cm−1 (Scheme 2). Moreover, the furan ring also Benzoxazine copolymers were prepared by curing F-Bz and
involves the curing process resulting in the formation of a S-Bz mixtures as shown in the Experimental Section. Figure 15
substituted furan ring in the polymer network. This is shown by displays the DSC thermograms, and Table 2 shows the Tg
the broadening of vibrations of the furan ring at 1589 cm−1. On values of the individual polymers and their copolymers. The
the other hand, there are close similarities in the FT-IR spectra glass transition temperature (Tg) is the temperature region
of the cured F-Bz and S-Bz mixture upon variation of the molar where the polymer transitions form a hard glassy material to a
ratio. These further imply that homogeneous copolymerization soft rubbery material. As benzoxazines are thermosetting mate-
occurred during the curing process.19,26,27 rials and chemically cross-link during the curing process, the
Figure 14 shows the 1H NMR spectra of the benzoxazine final cured material does not melt or reflow when heated (unlike
copolymer in an equimolar ratio [F-Bz/S-Bz (1:1)], which are thermoplastic materials) but undergoes a slight softening (phase
cured at 100, 150, 200, and 250 °C for 1 h. The spectrum at change) at elevated temperatures. As shown in the thermograms,
100 °C shows the characteristic peaks of the oxazine ring furfurylamine-based polybenzoxazine (PF-Bz) shows a Tg value of
protons at 4.95 and 4.92 ppm for the methylene protons of 148 °C when compared with stearylamine-based polybenzoxazine
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Table 2. DMA Data and Cross-Linking Density of PF-Bz, PS-Bz, and Their Copolymers
ε′ (GPa) Ve × 105 (mol m‑3)
sample no. sample mole ratio PS-Bz/PF-Bz initial at 50 °C Tg (°C) initial at 50 °C
1 a 1:0 2.82 2.53 101 3.7 3.5
2 b 3:1 2.94 2.71 106 4.0 3.6
3 c 1:1 3.12 2.98 125 4.1 3.9
4 d 1:3 3.29 3.13 154 4.4 4.1
5 e 0:1 3.33 3.15 148 4.4 4.1

Figure 17. DMA curves showing loss modulus of PF-Bz/PS-Bz

Figure 16. DMA curves showing storage modulus of PF-Bz/PS-Bz mixtures with various F-Bz contents in molar ratios (a) 0%, (b) 25%,
mixtures with various F-Bz contents in molar ratios (a) 0%, (b) 25%, (c) 50%, (d) 75%, and (e) 100%.
(c) 50%, (d) 75%, and (e) 100%.

(Tg of PS-Bz = 101 °C). Whereas for the copolymer mixtures, the shows the cross-linking density of the polymers. It is shown
one that contains the highest ratio of F-Bz (i.e., F75:S25) displays that cross-link density obviously increased with increasing F-Bz
a high Tg value of 154 °C. These results may be attributed to the content.
fact that the polybenzoxazine with a furan ring and the the co- Thermogravimetric analysis was used to study the thermal
polymer with an increased furan ring content increases the cross- stability of the polymers and its copolymers. The thermogram
linking density by means of its rigid backbone structure.19,28 in Figure 18 displays the initial degradation temperature (Ti),
There are a number of important material parameters that 5% weight loss temperature (T5), 10% weight loss temperature
can be derived from the DMA data. The initial storage modulus (T10), and char yield (CY) at 800 °C for the polymers and their
ε′ of a solid sample at room temperature provides a measure of copolymers. Among them, the furfurylamine-based polymer
the stiffness of the material under shear deformation. As shown (PF-Bz) shows the highest thermal stability [Ti, 349 °C; T5,
in Figure 16, the initial storage modulus of the PF-Bz is 3.33 361°C; and T10, 394 °C]. Whereas for the copolymers, the one
and that of PS-Bz is 2.82 GPa. The values are given in Table 2, that contains the high ratio of furfurylamine [F75:S25] has
which indicate that the storage moduli of the copolymers were the highest thermal stability [Ti, 328 °C; T5, 342 °C; and T10,
increased with increasing F-Bz content. The storage modulus of 376 °C].19,28 The presence of a furan ring structure had an
PF-Bz is superior when compared with PS-Bz because the furan enhancing effect on the degradation temperature of the copoly-
ring structure improved the cross-linking densities of polymers. benzoxazine of F-Bz and S-Bz by means of increasing the cross-
In addition, according to the tan δ plots of the polybenzox- linking density of the cured resin. The char yield of neat
azines in Figure 17, it can be found that the Tg values are 148 °C polybenzoxazine derived from F-Bz was 53.8%, which is much
for PF-Bz and 101 °C for PS-Bz, and for the copolymers, they higher than that of the polymer from S-Bz (about 23.9%).
increased from 106 to 154 °C. These values are close to those The limiting oxygen index (LOI) value, which is taken as an
obtained from the second scan of DSC (Tg values). indicator to evaluate the polymer’s flame retardancy,4 was
The cross-linking density of the polymers was calculated measured as shown in Table 3. The char yield of a material can
from the value of the storage modulus at room temperature and be used to estimate the LOI according to the Van Krevelen and
at 50 °C. Cross-link density is defined as the number of cross- Hoftyzer equation. LOI is defined as the minimum fraction of
link points per unit volume. The value of the cross-link density oxygen in a mixture of O2 and N2 that will support flaming
may be on the order of 10−3 to 10−5 mol/cm3 for a typical combustion.29 The LOI values calculated from the char yield
rubber material, corresponding to 15 to 1500 monomer units resulted from TGA analysis by using the following Van
between the cross-links. The cross-link density of the highly Krevelan and Hofytzer equation30
cross-linked thermoset can be determined by a modulus mea-
LOI = 17.5 + 0.4(CY)
surement using the following equation
Ve = ε′/3RT where LOI = limiting oxygen index, and CY = char yield (from
TGA data).
where ε′ = tensile storage modulus; T = temperature in K cor- The char yields of PF-Bz and S-Bz and their copolymers were
responding to storage modulus; and R = gas constant. Table 2 found to be high, in the range of 27−39%, indicating high flame
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ACS Sustainable Chemistry & Engineering

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Research Article

ACKNOWLEDGMENTS
The authors acknowledge the Department of Science and
Technology, New Delhi, and the Council of Scientific and
Industrial Research for funding this project. The authors also
acknowledge DST (FIST) and UGC (SAP) for the financial
support extended to procure instrumental facilities.

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