Reactive and Functional Polymers 143 (2019) 104344

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Reactive and Functional Polymers

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Synthesis of novel multi-functional fluorene-based benzoxazine resins: T

Polymerization behaviour, curing kinetics, and thermal properties
⁎ ⁎
Ting Wanga, Xuan-Yu Heb, Abdul Qadeer Dayoa,c, Jun-Yi Wanga, Jun Wanga, , Wen-bin Liua,
a
Key Laboratory of Superlight Material and Surface Technology of Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering
University, Harbin 150001, China
b
Xi'an Aerospace Composites Research Institute，Xi'an 710025, China
c
Department of Chemical Engineering, Balochistan University of Information Technology, Engineering and Management Sciences, Quetta 87300, Pakistan

A R T I C LE I N FO A B S T R A C T

Keywords: In this paper, a new series of novel aromatic multi-functional fluorene-based benzoxazine monomers (AMFB)
Fluorene-based benzoxazine were synthesized from the reaction of 9,9-bis(4-aminophenyl)-2,7-dihydroxy-fluorene, aniline, paraformalde-
Curing behavior hyde, and unsubstituted or substituted phenol including phenol, p-(tert-octyl)phenol, and nonylphenol, by two-
Curing kinetics stage Mannich condensation reactions. The structures of intermediates and the final benzoxazine monomers
Thermal properties
were identified via Fourier transform infrared (FTIR) and Hydrogen and Carbon nuclear magnetic resonance
(1HNMR and 13CNMR) analyses. The rheology, polymerization behaviour, curing kinetics, and thermal stability
of the obtained novel benzoxazines thermosets were measured by using rheometer, differential scanning ca-
lorimetry (DSC), FTIR, and thermogravimetric analysis (TGA), respectively. The o-nonyl phenol containing
fluorene-based benzoxazine monomer (t-BF-a-n) showed the best processability with the lowest curing energy
values. Moreover, the prepared polybenzoxazine thermosets showed excellent thermal stabilities and with
higher glass transition temperature (258–333 °C) than the traditional difunctional fluorene-based benzoxazine
resins.

1. Introduction on the properties of the thermosets [6–8]. Polybenzoxazine matrices

During the 20th century, phenolic resins were widely used in the
construction, electrical, electronic, and aerospace industries due to
their excellent mechanical strength, electrical properties, dimensional
stability, chemical corrosion resistance, less smoke emission, thermal
insulation, and flame retardancy. However, the phenolic resins have
practical application issues due to their inherent polymerization me-
chanism. For example, strong acidic or alkaline based catalysts are used
during the production process, which corrodes the equipment, and the
final products have obvious defects due to the volatile molecules pro-
duced during the curing process [1]. Therefore, polybenzoxazine, a new
type of polymer materials; was developed which not only has the in-
herent physical and mechanical properties of traditional phenolic resins
but can be cured without adding the catalyst [2,3]. Apart from these,
polybenzoxazine thermosets also have other advantages, such as low
porosity, low broadband dielectric loss, approximate zero shrinkage,
and so on [4,5]. Moreover, the polybenzoxazine resins have a very
flexible molecular design; several kinds of monomers can be obtained
by various combinations of phenols and amines; which ultimately effect
have broad application prospects in composite manufacturing, elec-
tronic packaging, insulation, and other fields [9–11].
Recently, the synthesis of multi-functional benzoxazine monomers
with three or more oxazine rings has attracted the industries due to the
excellent mechanical strength and thermal stabilities of the thermosets
[12,13]. Multicomponent star-shaped benzoxazine compounds with
inorganic constituents are also reported in the literature [14–16]. The
fluorene-based benzoxazine resins are one of the easy and economical
ways to achieve multi-functional benzoxazine. A series of epoxy,
polyimide, polycarbonate, and benzoxazine resins having fluorene
molecule in the structure are prepared. Thermosets showed good heat
resistance, excellent thermal stabilities, dielectric properties, good
mechanical properties, high transparency, and refractive index
[17–26]. However, the fluorene molecule exists as an overhang side
group in these resins, which increases the polymer chain rigidity and
curing temperature, the ultimate thermosets showed very poor tough-
ness with higher brittleness. Therefore, it is necessary to redesign the
molecular structure to improve the properties of polymers.
In this paper, asymmetric fluorene-based benzoxazine monomers

⁎
Corresponding authors.
E-mail addresses: wj6267@hrbeu.edu.cn (J. Wang), liuwenbin@hrbeu.edu.cn (W.-b. Liu).

https://doi.org/10.1016/j.reactfunctpolym.2019.104344
Received 17 May 2019; Received in revised form 31 July 2019; Accepted 22 August 2019
Available online 23 August 2019
1381-5148/ © 2019 Elsevier B.V. All rights reserved.
T. Wang, et al.
were prepared via two-stage Mannich condensation methods. The
phenolic compounds used for the synthesis of the monomers contain p-
tert-octyl or o-nonyl chain on the phenol. The detailed synthesis,
polymerization behaviour, curing kinetics, and thermal properties of
the polymers are investigated.
2. Experimental
2.1. Materials
2,7-dihydroxy-9-fluorenone, methylsulfonic acid, sodium borohy-
dride, and p-formaldehyde were obtained from Shanghai Jingchun
Reagent Co., Ltd. (Shanghai, China). Xylene and n-hexane were pro-
cured from Shandong Haobo Biomaterials Co., Ltd. (Shandong, China).
Aniline, formic acid, acetic acid, ethanol, tetrahydrofuran (THF), di-
chloromethane, and trichloromethane were purchased from Tianjin
Kermel Chemical Reagent Co., Ltd. (Tianjin, China). Phenol, p-tert-octyl
phenol, and o-nonylphenol were obtained from Tianjin Komeo
Chemical Reagent Co., Ltd.(Tianjin, China). Tianjin Fuyu Fine Chemical
Co., Ltd. (Tianjin, China) supplied the trifluoroacetic anhydride, ethyl
acetate, sodium carbonate, and sodium bicarbonate. All the chemicals
used in the study were of AR grade and used as received without pur-
ification.
2.2. Preparation ofAMFB monomers
The route followed for the synthesis of AMFB monomers is shown in
Scheme 1.
2.2.1. Preparation of9,9-bis(4-aminophenyl)-2,7-dihydroxy-fluorene
The 9,9-bis(4-aminophenyl)-2,7-dihydroxy-fluorene (BADHF) was
prepared by the reaction of 2,7-dihydroxy-9-fluorenone with aniline.
The followed method for the synthesis method is already discussed in
detail in our earlier published article [27].
2.2.2. Preparation of fluorenyl monomer having trifluoroimide protective
group (b-PAHF)
BADHF (0.05 mol, 17.4 g) and THF (100 mL) were poured into a
250 mL three-neck flask and stirred for 15 min in an ice-water bath.
Then, the trifluoroacetic anhydride (0.15 mol, 10.5 g) was added
dropwise, and the solution was reacted at room temperature for 2.5 h.
After the reaction, the THF was evaporated under vacuum, and ethyl
acetate (200 mL) was added. The solution was washed five times with
saturated aqueous sodium bicarbonate solution and three times with
distilled water. Finally, the organic phase and solvent were removed by
rotary evaporation to obtain the pale red powder and dried under va-
cuum at 80 °C. The yield of b-PAHF powder was 92%.
2.2.3. Preparation of bisphenol benzoxazine monomer containing
trifluoroimide protective group (b-PABF-a)
A mixture was prepared by mixing b-PAHF (0.01 mol, g), aniline
(0.02 mol), p-formaldehyde (0.06 mol, g), chlorobenzene (15 mL), and
xylene (15 mL) into a 250 mL three-neck flask and reacted at 130 °C for
4 h, and cooled to room temperature. The n-hexane (100 mL) was added
and the produced precipitates were filtered and dissolved in di-
chloromethane. Hereafter, the dichloromethane was removed by the
alkali washing with 0.5 mol/L sodium carbonate solution, water
washing, and rotary evaporation. Finally, the light yellow powder (b-
PABF-a) was obtained (yield 86%) after vacuum drying at 80 °C.
2.2.4. Preparation of bisphenol benzoxazine monomer containing primary
amine group (b-ABF-a)
A mixture of b-PABF-a (0.09 mol), sodium borohydride (0.45 mol),
methanol (2 mL), and ethyl acetate (200 mL) was prepared in a 250 mL
three-neck flask, and the solution was stirred for 5 h at room tem-
perature in nitrogen (N2) atmosphere. Later, the solution was washed
2
Reactive and Functional Polymers 143 (2019) 104344
several times with saturated NaCl solution (100 mL), and the solvents
were removed by water washing and rotary evaporation. The light
yellow solid withan81% yield was obtained.
2.2.5. Preparation ofAMFB monomers
Phenol (0.01 mol), p-formaldehyde (0.03 mol), b-ABF-a (0.005 mol),
and xylene (20 mL) were added to a 250 mL three-neck flask and re-
acted at 130 °C for 4 h, and cooled to room temperature. The pre-
cipitates were produced after adding n-hexane. The produced pre-
cipitates were filtered, several times washed with ethanol and dried in a
vacuum dryer at 60 °C for 24 h to obtain the phenol-based aromatic
multi-functional fluorene-based benzoxazine monomer (t-BF-a-p). The
yield of the t-BF-a-p monomer was 61%.
The same procedure was followed for the synthesis of other phenolic
compounds only phenol was substituted by p-tert-octyl phenol or o-
nonylphenol. The prepared monomers were represented as t-BF-a-o, and
t-BF-a-n, respectively.
2.3. Curing of benzoxazine resins
AMFB monomers were melted and shifted to steel molds having
definite test shape; subsequently, the samples were isothermally cured
in an air-dry oven. The samples were cured at 150, 180, 210, and 240 °C
for 2 h at each stage. Finally, the cured thermosets were cooled to room
temperature and polished to the appropriate test specifications using
the sandpaper. After each curing stage, the DSC and FTIR analyses were
performed to evaluate the curing behaviour. In the meanwhile, the
completely cured thermoset samples were used to evaluate their
thermal stability resistance using the TGA test.
2.4. Characterization methods
Fourier transform infrared spectroscopy (FTIR) spectra from 500 to
4000 cm−1 wavenumber were recorded on a PE Instruments spotlight
400 FTIR spectrometer. Proton and carbon nuclear magnetic resonance
(1HNMR and 13CNMR) spectra were produced after dissolving the
samples in DMSO-d6 solution on a Bruker AVANCE 500 spectrometer at
500 MHz. Differential scanning calorimetry (DSC) test was performed at
a 10 °C·min−1 heating rate on a Q-200 differential scanning calori-
meter, TA Instruments, USA, from 20 to 380 °C in 50 mL min−1N2 flow.
The rheological behaviors of the monomers and prepolymer were in-
vestigated at 10 s relaxation time and 3.259 Pa pressure by using a
dynamic rheometer AR-2000ex, TA Instruments, USA, with a 1 Hz
frequency, and 4 °C min−1as the heating rate. Thermogravimetric
analysis (TGA) was performed using a thermogravimetric analyzer Q50,
TA Instruments, USA, at a heating rate of 10 °C min−1 under N2 or air
supply at 50 mL min−1 flow rate.
3. Results and discussion
3.1. Structural characterization of intermediates and AMFB monomers
The FTIR spectra of intermediates and AMFB monomers are pro-
duced in Fig. 1. From the BADHF spectrum in Fig. 1(A), we can easily
observe the benzene ring skeleton absorption at 1611 and 1511 cm−1
peaks. The bending absorption of CeN was observed at 1182 cm−1. In
addition, the absence of 1700 cm−1peak assigned to C]O stretching
vibration peak of 2,7-dihydroxyfluorenone indicates that the reaction
was completed. The spectrum of b-PAHF intermediate shows the broad
overlapping peak in 3100–3600 cm−1, this peak indicates the of NeH
and OeH stretching vibration peaks of the trifluoroimide group, and
the absorption signal at 1704 cm−1 is ascribed to the stretching vibra-
tion of carbonyl (C]O) groups, which indicates that the amino group in
BADHF has been replaced by trifluoroimide group.
The spectrum of b-PABF-a shows the NeH stretching vibration peak
at 3297 cm−1. The characteristic absorption at 1711 cm−1 was ascribed
T. Wang, et al. Reactive and Functional Polymers 143 (2019) 104344

H 2N NH2
O NH2
CH3SO3H
+ o
HO OH 150 C, 14h
HO OH

H H
F3C N N CF3
H H NH2 C C
H 2N NH2 F3C N N CF3
C C O O
O O + (CH2O)n
TFAA O O
HO OH THF 0 oC, 2.5 h HO OH CB/Xylene 130 C, 4 h
o
N N

BADHF
b-PAHF b-PABF-a

O O
H 2N NH2 R R
OH N N
R
+ (CH2O)n
NaBH4
O O o
EtOAc/EtOH rt, 5 h Xylene 130 C, 4 h O O
N N
N N

b-ABF-a
AMFB

C9H19 C9H19
O O O O O O

N N N N N N

O O O O O O

N N N N N N

t-BF-a-p t-BF-a-o t-BF-a-n

Scheme 1. The route followed for the synthesis of AMFB monomers.

to C]O stretching vibration. The characteristic absorption peak of
1,2,4,5- tetrasubstituted benzene was observed at 1478 cm−1. In ad-
dition to this, the stretching vibration of ether bonds (CeOeC) was
noticed at 1244 cm−1 absorption peak, and the CeH out-of-plane
bending vibration in the benzene ring was recorded at 950 cm−1. These
peaks confirm that the benzoxazine ring in the b-PABF-a monomer. The
NeH stretching vibration peak of the primary amine was spotted at
3363 cm−1 in the b-ABF-a monomer sample. Moreover, the absence of
carbonyl (C]O) stretching vibration peak at 1700 cm−1 indicates that
the trifluoroimide protective group was completely removed after the
sodium borohydride reaction.
In Fig. 1(B), the absorption peak at 3032 cm−1 corresponds to the
stretching vibration of the unsaturated CeH bond in the benzene ring.
The stretching vibration peak at 2910 cm−1 belongs to the saturated
alkyl CeH bond. The oscillating peaks of methylene on the oxazine ring
were observed at 1368 and 1338 cm−1, and the peaks at 1224 and
1253 cm−1 showed the asymmetric stretching vibration of CeOeC
bond, while the symmetrical stretching vibration of CeOeC bond was
detected at 1110 cm−1. The asymmetric stretching vibration peak of
CeNeC bond was located at 1158 cm−1. The benzoxazine ring was
confirmed by the detection of CeH out-of-plane bending vibration in
the phenyl at 928–943 cm−1 peak. These results confirm that the
monomers contain a benzoxazine structure [28]. The FTIR spectrum of
t-BF-a-o monomer was nearly similar to the FTIR spectrum of t-BF-a-p,
only have broad peaks of the saturated CeH stretching vibration from
3100 to 2800 cm−1. In addition to this, the FTIR spectrum of t-BF-a-n
monomer was similar to the FTIR spectrum of t-BF-a-o monomer but has
a very broad –OH stretching vibration peak of adsorbed water mole-
cules at 3416 cm−1.
The 1H and 13C NMR spectra of intermediates monomers are plotted
in Fig. S1. In Fig. S1(A), the hydroxyl proton on the phenyl ring was
detected at a 9.26 ppm. The chemical shift of the phenyl proton was
observed at 6.40–7.45 ppm. The 4.93 ppm peak is attributed to the
amino group proton in the BADHF. The b-PAHF intermediate shows the
chemical shift of the secondary amine protons of the trifluoride imide
was observed at 11.24 ppm. In addition to this, the hydroxyl proton on
the benzene ring was observed at 9.44 ppm, and protons of the benzene
ring were observed by the chemical shift at 6.71–7.58 ppm.
After the first Mannich condensation reaction, 9.44 ppm peak re-
presenting the phenolic hydroxyl proton disappear. In addition, the

3
T. Wang, et al. Reactive and Functional Polymers 143 (2019) 104344

Fig. 2. The 1HNMR (A) and 13

CNMR (B) spectra of AMFB monomers.
Fig. 1. The FTIR spectra of intermediates (A) and AMFB monomers (B).

atom in fluorene ring.

oxazine ring characteristic peaks of OeCH2eN and AreCH2eN were
The 1H and 13CNMR spectra of t-BF-a-p and other new benzoxazine
observed at 5.44 and 4.74 ppm, respectively, which confirm the suc-
monomers are displayed in Fig. 2. The phenyl ring hydrogen atoms
cessful synthesis of b-PABF-a monomer. Moreover, the proton peaks
were detected at 6.60–7.43 ppm, while the oxazine ring characteristic
(δ = 11.24 ppm) of secondary amine in trifluoride imide do not change
absorption peaks of NeCH2eAr and OeCH2eN were observed at
significantly. After the removal of the trifluoride imide group from b-
4.56–4.70 and 5.33–5.40 ppm, respectively. The NeCH2eAr and
PABF-a monomer via the action of sodium borohydride, the proton
OeCH2eN characteristic absorption peaks indicate that there are two
peak (δ = 11.24 ppm) of secondary amine on trifluoride imide was
kinds of oxazine ring structures in the monomer, indicating that the
completely disappeared. The proton of oxazine ring characteristic peaks
target product t-BF-a-p was obtained. In addition to this, additional
of OeCH2eN and AreCH2eN were observed at 5.41 and 4.70 ppm,
peaks were observed depending on the phenol, such as the t-BF-a-o
respectively. Moreover, a new proton peak at 4.89 ppm, which corre-
monomer shows the protons of tert-octyl from 0.67 to 1.63 ppm. The t-
sponds to the amino group on the phenyl ring, was observed, this
BF-a-n monomer produced the peaks of hydrogen protons of nonyl
confirmed that the b-ABF-a monomer is formed.
13 group from 0.40 to 0.81 ppm.
CNMR spectra of all the intermediates are displayed in Fig. S1(B).
The 13CNMR spectra of t-BF-a-p and other new benzoxazine
For BADHF, the single peaks located at 147.8 and 152.3 ppm are as-
monomers are displayed in Fig. 2(B). The chemical shifts at 93.2–93.6
signed to the carbon atom resonances of CeNH2 and CeOH, respec-
and 59.4–59.7 ppm are assigned to the carbon atom resonances of
tively. For b-PABF, the multiple peaks around 115.6 ppm are attributed
OeCH2eN and AreCH2eN of oxazine rings, respectively. In particular,
to the carbon atom resonances of eCF3 and the single peak located at
there are four kinds of carbon atom resonances corresponding to bi-
153.2 ppm is assigned to the carbon atom resonances of C]O. For b-
sphenol-type oxazine rings (59.55 and 93. 2 ppm) and diamine-type
PABF-a, the peak at 63.5 ppm is described to the quaternary carbon
oxazine rings (59.7 and 93.6 ppm) existing in t-BF-a-p monomer

4
T. Wang, et al.
Fig. 3. The relationship between dynamic viscosity and temperature of AMFB
monomers.
backbone. The peaks around 63.5 ppm are ascribed to the quaternary
carbon atom in fluorene ring. The analysis of 13CNMR spectra of t-BF-a-
o and t-BF-a-n monomer were nearly similar to the 13CNMR spectrum of
t-BF-a-p.
The obtained FTIR,1H and 13C NMR spectra are in good agreement
with the proposed molecular structure. In connection with the analysis,
we can suggest that all the intermediates and AMFB monomers are
successfully synthesized.
3.2. Rheological properties
The viscosity variation of AMFB was determined as a function of
temperature from 50 to 250 °C, and the produced curves are illustrated
in Fig. 3. In order to compare the technological properties of different
AMFB monomers, the softening point and gel point temperatures were
determined at 1000 Pa·s viscosity. The monomer's processing window
was calculated from the difference of gel point and softening point
temperatures [29,30].
We can easily observe from the plot that all the AMFB monomers
were in a solid state at room temperature and gradually melted as the
temperature was increased. Among the studied AMFB monomers, the t-
BF-a-n monomer has the lowest softening point temperature (123 °C).
This is due to the fact that the melting points of benzoxazine monomers
decrease with an increase in the alkyl chain length in the monomer
structure.
Generally speaking, the branched polymer has two effects on visc-
osity. First, when the branched-chain is quite short, the viscosity is
much lower than that of the straight-chain molecules with the same
molecular weight, and it is easy to flow. If the branched-chain is very
long, the viscosity is much higher than that of the straight-chain mo-
lecules with the same molecular weight. Secondly, the effect of the
number of branched chains on the viscosity is similar to the above.
When the molecular weight is equal, the shorter the branched-chain is,
the smaller the steric resistance is, which leads to high resistance, low
viscosity, and easy flow. If there are fewer branched chains, the longer
branched chains shows greater the steric resistance, resulting in smaller
resistance, higher viscosity, and less flow [37]. So, the t-BF-a-o
monomer has the octyl group with branched structure, which creates
the steric hindrance and greatly restricts the molecular movement, and
in the result, the monomer has higher viscosity and softening point
temperature (151 °C). The t-BF-a-p monomer did not reach to softening
point temperature and the lowest viscosity value of 1678 Pa·s was
5
Reactive and Functional Polymers 143 (2019) 104344
Fig. 4. DSC thermograms of AMFB polymers.
recorded at 140 °C. Furthermore, the t-BF-a-p monomer showed the
increased in the viscosity value (gelation point) to early when relatively
compared to other monomers. The t-BF-a-p monomer does not have any
substituted alkyl groups in the molecule structure, and as the tem-
perature was increased, the cross-linking reaction simultaneously oc-
curred on ortho and para position of phenolic hydroxyl. Therefore, the
t-BF-a-p monomer has the highest reaction activity and can be cured at
a slightly lower temperature.
As we know that the octyl group of t-BF-a-o monomer and nonyl
group of t-BF-a-n monomer are attached at para and ortho positions of
phenolic hydroxyl, respectively. The reaction activity of the ortho po-
sition is much higher than that of the para position, so, the t-BF-a-o
monomer has higher reactivity and reaches the gel point temperature
firstly. From the above plot, the processing window of the t-BF-a-p, t-BF-
a-n, and t-BF-a-o monomers was calculated to be 10, 21, and 65 °C,
respectively.
3.3. Polymerization behavior
3.3.1. DSC study
The dynamic DSC thermograms of AMFB polymers are shown in
Fig. 4. The dynamic DSC of pristine AMFB monomers before and after
each curing stage was evaluated, and the produced curves are shown in
Fig. 5. In addition to this, the curing degree of the AMFB monomer after
each curing stage is shown in Table 1.
From the DSC curves of the neat monomers, we can easily analyze
that all the AMFB monomers showed a sharp exothermic peak. These
exothermic peaks correspond to the ring-opening polymerization of the
monomer. The exothermic peak temperatures of t-BF-a-p, t-BF-a-o, and
t-BF-a-n monomers were observed at 264, 267, and 270 °C, respectively.
In addition to this, the initial polymerization temperatures were in the
range of 210–220 °C, which show that the synthesized AMFB monomers
follow the thermal ring-opening mechanism of 1,3-benzoxazine. The
lowest exothermic peak temperature was observed for t-BF-a-p
monomer, while the t-BF-a-n monomer showed the highest exothermic
peak temperature. This shows that the t-BF-a-p monomer has higher
reactivity, as it does not contain any substituent group on the phenolic
hydroxyl, both ortho and para position can participate in the cross-
linking reaction during the thermal ring-opening polymerization. While
the t-BF-a-n monomer has lower reactivity as the ortho position con-
tains long-chain alkyl, the reaction can only take place on the para
position of phenolic hydroxyl, and the para position has lower activity
[31]. However, the t-BF-a-o monomer has moderate value even it
T. Wang, et al.
Fig. 5. DSC thermograms of AMFB monomers after isothermal curing at dif-
ferent temperatures, t-BF-a-p (A), t-BF-a-o (B) and t-BF-a-n (C).
6
Reactive and Functional Polymers 143 (2019) 104344
Table 1
The curing degree of monomers after isothermal curing at different tempera-
tures.
Monomer Curing degree (%)
150 °C 180 °C 210 °C
t-BF-a-p 18.3 56.4 83.7
t-BF-a-o 3.9 63.0 87.1
t-BF-a-n 34.7 63.1 84.9
contains the branched octyl structure on the para position, and the
branched octyl structure may hinder the formation of cross-linking
network structure [25]. Moreover, form the embedded DSC data in
Fig. 5, we can observe that as the length of the substituted alkyl chain
length was increased, a decrease in the exothermic enthalpy value was
recorded. These declines in the enthalpy values can be dedicated to the
dilution behavior of the alkyl chain on the oxazine ring concentration.
The t-BF-a-o monomer also shows a small heat absorption peak corre-
sponding to the melting point at 153 °C.
It can be seen that the exothermic enthalpies of all the AMFB
monomers decrease and percentage of the curing degree increase as the
curing stage proceeds to the next temperature level. This confirms that
the number of non-reacted functional groups in benzoxazine monomers
resin decreases continuously with the increasing curing degree. After
the isothermal curing at 210 °C, the curing degree of all the monomers
exceeds 83%. After the final curing stage at 240 °C, the exothermic peak
was not observed in all the synthesized monomers.This confirms that
the polymer does not contain any uncured benzoxazine groups.
In addition, the DSC curves showed that, after each curing stage, the
exothermic peak temperature moved to higher temperatures due to the
formed network structures and increased curing degree. The activity of
the functional group in the system is significantly hindered by the
formed cross-linking network and reduced the polymerization rate.
Moreover, an increase in the temperature reduced the system viscosity
and increased the reactivity of functional groups, and ultimately, the
complete curing can be achieved at higher temperatures [31,32].
The glass transition temperatures (Tg) of the fluorene-based poly-
benzoxazines were observed after complete curing procedure, the va-
lues for poly(t-BF-a-p), poly(t-BF-a-o) and poly(t-BF-a-n) were recorded
at 338, 328 and 256 °C, respectively. From the Tg, we can see that the
long nonyl chain containing poly(t-BF-a-n) has the lowest values, while
the simple phenol-based poly(t-BF-a-p) has the highest Tg value. The
fluorine molecule is rigid and the addition of the molecule in molecular
backbone restrains the internal rotations of the polymer segments. In
addition to this, the Tg value of all the prepared thermosets are much
higher than the typical bifunctional fluorene-based polybenzoxazine
(poly(BF-p), 242 °C by the DSC test) [25], and the Tg values were much
lower than the furan-containing tetrafunctional fluorene-based ben-
zoxazine (poly(t-BF-f), 440 °C by the DMA test) [27].
3.3.2. FTIR study
The FTIR spectra of all the synthesized AMFB monomers after iso-
thermal heating at different curing temperatures are shown in Fig. 6.
The FTIR spectra from 4000 to 2000 cm−1 of all the AMFB mono-
mers after different curing stages are nearly similar to each other. As
can be seen, the oxazine ring characteristic peak at 928–943 cm−1of t-
BF-a-p monomer has been greatly reduced after heating at 180 °C. The
strength of the oscillating vibration peaks of methylene on the oxazine
ring at 1368 and 1338 cm−1, the CeOeC stretching peaks at 1253 and
1224 cm−1, and the CeNeC vibration peaks at 1158 and
1110 cm−1gradually decreased as the curing proceeds, and can com-
pletely disappear after curing at 240 °C. In addition to this, after the
oxazine ring-opening, the AreOH characteristic absorption peak ap-
peared at 3371 cm−1, which indicated that the oxazine ring was opened
and formed CeO bond at higher temperatures. After curing at 240 °C,
T. Wang, et al. Reactive and Functional Polymers 143 (2019) 104344

the benzoxazine monomers were completely cured, these results are

inconsistent with the DSC results. Moreover, the intermolecular and
intramolecular hydrogen bond in the polybenzoxazine network struc-
tures were observed by the broad peak at 3200–3600 cm−1. The ex-
pected intermolecular and intramolecular hydrogen bond include
eOH⋯O (3320–3400 cm−1), eOH⋯π (3550–3600 cm−1), eOH⋯O
(3430–3470 cm−1), and eOH⋯N (3140–3190 cm−1), and so on [31].

3.4. Curing kinetics of AMFB monomers

As can be seen, the DSC curves of curing reactions are conducted at

different heating rates of 5, 10, 15, and 20 °C·min−1, with exothermic
peaks appearing at different temperatures. In this study, the activation
energy (Ek, Eo) is calculated by the Kissinger and Ozawa methods using
Eqs. (1) and (2) [33].

⎛ β ⎞ AR E
− k
ln ⎜ 2 ⎟ = ln
T
⎝ ⎠p Ek RT p (1)

AE E
ln(β ) = ln ⎛ o ⎞ − ln F (α ) − 1.052 ⎛ o ⎞
⎝ R ⎠ ⎝ RT ⎠ (2)
here, the Ek and Eo show the activation energy calculated by Kissinger
and Ozawa methods, respectively, while the β, Tp, R, F(α) represent the
heating rate, peak exotherm temperature (K), the universal gas con-
stant, and constant function, respectively.
The value of activation energy can be calculated from the ln (β/Tp2)
versus 1/Tp plot, where the slope of the plot show (−Ek/R) in the case
of Kissinger method. While the Ozawa method calculation needs lnβ
versus 1/Tp plot, and the slope of the plots represents the (−1.052(Eo/
R)).
The DSC scanning curves of all the synthesized AMFB monomers at
different heating rates are shown in Fig. 7.
From the dynamic DSC test curves, we can easily evaluate that the
curing exothermic peaks of the all the benzoxazine monomer moved
towards the higher temperatures and the peak height increased as the
heating rate of the DSC was increased. On the lower heating rate, the
monomers have sufficient time for curing reaction, as the DSC scanning
rate was increased, the time of curing reaction was reduced, and the
thermal effect of the reaction increased in unit time, the thermal inertia
increases, and the exothermic peak temperature moved towards the
higher temperatures.

3.4.1. Kissinger and Ozawa methods

The linear regression curves of Kissinger and Ozawa methods for all
the synthesized AMFB benzoxazine monomers are shown in Fig. S2, and
the apparent activation energy values obtained from Kissinger and
Ozawa methods are summarized in Table 2.
Both Kissinger and Ozawa linear regression curves for all the AMFB
monomers showed a good linear relationship. The calculated apparent
activation energies for the benzoxazine monomer's curing reactions
were in the range of 132.6–145.4 kJ/mol by Kissinger method and
134.5–146.5 kJ/mol by Ozawa method. The activation energy values of
studied benzoxazine monomers decrease significantly with the increase
in the alkyl chain length. This is because of the longer alkyl chain
monomer has lower viscosity, which improves the curing reaction.

3.4.2. Starink method

Starink proposes an accurate method after modifying the
Flynn–Wall–Ozawa and Kissinger–Akahira–Sunose methods for the
calculation of the conversion rate (α). The Starink equation is as follow
[34].

βi ⎞ Ea
Fig. 6. The FTIR spectra of AMFB monomers after isothermal curing at different ln ⎛⎜ 1.92 ⎟ = Const − 1.0008
temperatures, t-BF-a-p (A), t-BF-a-o (B) and t-BF-a-n (C). T
⎝ a, i ⎠ RTa, i (3)
The relationship between conversion (α) of AMFB monomer against

7
T. Wang, et al. Reactive and Functional Polymers 143 (2019) 104344

Table 2
The apparent activation energies calculated using the Kissinger and Ozawa
methods.
Samples Ek (kJ/mol) Eo (kJ/mol)

t-BF-a-p 145.4 146.5

t-BF-a-o 138.9 140.4
t-BF-a-n 135.3 137.0

Fig. 8. TGA thermograms of AMFB polymers under nitrogen atmosphere.

Table 3
Thermal stability parameters of cured AMFB thermosets.
Samples T5 (°C) T10 (°C) Yc (%, 800 °C) Reference

Poly(t-BF-a-p) 347 395 58.1 Current work

Poly(t-BF-a-o) 344 379 52.9 Current work
Poly(t-BF-a-n) 336 377 48.0 Current work
Poly(B-bbf) 329 351 36.3 [36]
Poly(B-obf) 316 331 18.5 [36]
Poly(BABPF-p) 380 399 47.0 [31]

temperature is shown in Fig. S3.

From Fig. S3 plots, we can easily observe that all the curves of AMFB
monomers, even on different scanning rate; show an “S” shape, sug-
gesting that the curing reaction of the monomer is an autocatalytic
reaction. In the initial curing reaction stage, the conversion rate
changed slowly with the rise in the temperature, latera sharp en-
hancement in the conversion rate was observed as the temperature of
the system was increased to higher temperatures. This forms the cross-
linking network in the polymer structure and increases the viscosity,
which reduced the molecular movement and the collision between
functional groups became extremely difficult. After a certain extent of
conversion rate, the curing reaction gradually changes from chemical
control to diffusion control, and the conversion curves become flatter.
The corresponding temperature values of α (0.05, 0.10, 0.15,
0.20……0.90, 0.95) at different heating rates can be obtained from the
relationship between α and T of AMFB monomers. The fitting curve of
ln(β/Tf1.92) and 1/Tf at different heating rates are devised by Starink
equation. Fig. S4 illustrates the linear relationship of ln(β/Tf1.92) versus
1/Tf with a slope of −1.0008(Ea/R). The value of activation energy can
be calculated from the slope. The relationship between Ea and α is
shown in Fig. S5.
Fig. 7. Dynamic DSC thermograms of t-BF-a-p (A), t-BF-a-o (B) and t-BF-a-n (C)
From the Ea v/s α plot, we can easily observe that the Ea of t-BF-a-p
monomers at different heating rates.
monomer decreases with the increase of conversion at the initial

8
T. Wang, et al.
reaction stage (α < 0.2), mainly due to the viscosity of monomer was
reduced as the temperature was increased. However, the behaviors oft-
BF-a-o and t-BF-a-n monomers were opposite to the behavior oft-BF-a-p
monomer. This is due to the fact that these two kinds of monomers were
in the complete melting state before polymerization, and their viscos-
ities were lowest as discussed earlier in the rheological properties sec-
tion. When the polymerization starts, the system viscosities increase
suddenly due to the gelation. At the intermediate reaction stage, the Ea
of all the curing systems changes little. On α > 0.6, the Ea of all the
systems increases with the increase of conversion. This is due to the
formation of large three-dimensional network structures after the ox-
azine ring-opening, which reduced the functional groups and chain
segments activities. The polymerization process gradually changes from
chemical control to diffusion control, which obviously increases the Ea.
3.5. Thermal stabilities
The thermogravimetric curves of AMFB polymers are plotted in
Fig. 8. The extracted data from the TGA plot, such as the 5 and 10
weight percentage loss temperatures (T5 and T10) and carbon residue
rate (Yc) at 800 °C, are summarized in Table 3.
The evaluation of TGA curves showed that the initial thermal de-
composition temperatures (T5 and T10) of AMFB polymers were in the
range of 336–360 and 377–405 °C, respectively, and the Yc were re-
corded in 34.9–58.1% range. These thermal stability results are sig-
nificantly higher than that of bisphenol A-aniline based poly-
benzoxazine resin (i.e., T5: 277 °C, T10: 317 °C, and Yc: 33.2%) [35].
These enhancements in the thermal stability values are due to the in-
troduction of heat resistance fluorene ring in the polymers. The increase
in the number of functional sights in the monomer can improve the
cross-linking and effectively reduce the share of unstable end groups in
polymers.
The T5, and T10 thermal parameters of the poly(t-BF-a-p) were best
among the studied polybenzoxazine thermosets and recorded as 347
and 395 °C, respectively. These values are higher than the corre-
sponding T5 and T10 values of bisphenol fluorene-aniline based ben-
zoxazine (poly(B-bbf) and poly(B-obf)) [36], and lower than the dia-
mine-fluorene based benzoxazine resin (poly(BABPF-p)) [31], however,
the Yc value was much higher. These enhancements can be dedicated to
the increased number of the oxazine ring, which significantly improved
the crosslinking density of polybenzoxazine thermosets. However, the
excessive introduction leads to the generation of more CH2eNeCH2
flexible segments in the network structures, which resulting in the de-
cline of initial thermal decomposition temperatures [31,36]. A large
number of aromatic rings produce a higher value of carbon residue.
4. Conclusions
In this current study, three different fluorine-based benzoxazine
monomers were prepared with different aliphatic chains lengths and
substitution sites. The effects of aliphatic chains lengths and substitu-
tion sites on the curing kinetics, behavior, and rheological and thermal
properties were studied. The synthesized AMFB benzoxazine monomers
have higher softening point temperature and narrower processing
window. The activation energies calculated by Kissinger and Ozawa
methods showed that the value was significantly reduced as the alkyl
chain length was increased, and recorded in the range of 108.1–145.4
and 110.8–146.5 kJ/mol, respectively. The glass transition tempera-
tures of the synthesized thermosets were higher than the bifunctional
fluorene-based benzoxazines. All the AMFB monomers have excellent
thermal stability. The initial thermal decomposition temperature and
char yield at 800 °C are higher than those of bisphenol A-aniline and
bisphenol fluorenyl polybenzoxazine resins.
9
Reactive and Functional Polymers 143 (2019) 104344
Acknowledgments
This work is financially sponsored by the National Natural Science
Foundation of China (Project No.51773048), Natural Science
Foundation of Heilongjiang Province (Project No.E2017022), and
Fundamental Research Funds for the Central Universities (Project
No.HEUCFP201724).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.reactfunctpolym.2019.104344.
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