J Therm Anal Calorim (2015) 119:19131921
DOI 10.1007/s10973-014-4294-1
Synthesis, curing behavior, and thermal properties of fluorene-
based benzoxazine-endcapped copoly(ether ketone ketone)s
Hui Wang Jun Wang Tian-tian Feng
Noureddine Ramdani Yue Li Xiao-dong Xu
Wen-bin Liu
Received: 5 September 2014 / Accepted: 4 November 2014 / Published online: 2 December 2014
Akademiai Kiado, Budapest, Hungary 2014
Abstract A series of fluorene-based benzoxazine-end-
capped copoly(ether ketone ketone)s (co-PEKKs) were
successfully synthesized, in which the co-PEKKs were
prepared with different molar ratios of 2,7-dihydroxy-9-
fluorenone to bisphenol-A. The obtained phenol-ended co-
PEKKs reacted with formaldehyde and n-butylamine to
yield the benzoxazine-endcapped co-PEKKs (B-PEKKs).
The structure of these oligomers was studied by Fourier
transform infrared spectroscopy and 1H nuclear magnetic
resonance spectroscopy, and the molecular mass of these
phenol-ended co-PEKKs was detected by gel permeation
chromatography. The thermal behaviors of these B-PEKKs
were determined by differential scanning calorimetry. In
addition, the thermal and dynamic mechanical properties of
the polymer films were investigated by thermogravimetric
analysis and dynamic mechanical analysis. The results
indicate that the incorporation of co-PEKKs within the
benzoxazine backbone considerably improves the tough-
ness of the fluorene-containing polybenzoxazines without
much sacrifice of their thermal properties. Furthermore, as
the content of 2,7-dihydroxy-9-fluorenone increases, the T5
values decrease, while the Tg values and char yields of the
prepared polymers increase to reach their highest values at
256 C and 64 %, respectively.
H. Wang  J. Wang (&)  T. Feng  N. Ramdani 
Y. Li  X. Xu  W. Liu (&)
Polymer Materials Research Center, Key Laboratory of
Superlight Material and Surface Technology of Ministry of
Education, College of Materials Science and Chemical
Engineering, Harbin Engineering University, Harbin 150001,
Peoples Republic of China
e-mail: wj6267@sina.com
W. Liu
e-mail: wjlwb@163.com
Keywords Fluorene-based polybenzoxazines 
Copoly(ether ketone ketone)  Polymerization behavior 
Thermal properties
Introduction
Over the past few decades, polybenzoxazines, as recently
developed phenolic resins, have received much interest in
academia and industries. They provide various attractive
properties that cannot be afforded by traditional phenolic
resins and epoxies, such as high thermal stability, high char
yields, high glass transition temperature (Tg), low flam-
mability, low absorption of water, and low dielectric con-
stant [17]. Another attractive aspect of benzoxazine
compounds is that they can be prepared from inexpensive
raw materials like phenol, primary amine, and formalde-
hyde. Therefore, the wide ranges of these raw materials
allow tremendous molecular-design flexibility for the
benzoxazine precursor [813]. Polybenzoxazines are
polymerized via a thermal ring-opening polymerization
reaction of the corresponding benzoxazine monomers without
the addition of any extra catalysts and without generating any
byproduct or volatiles, and thus offer an excellent dimensional
stability for their cured products [1417].
Various studies have been carried out to enhance the
outstanding thermal properties of polybenzoxazines. The
incorporation of rigid groups or other thermosetting resins
can improve the thermal properties of polybenzoxazines,
and the introduction of fluorene moieties into benzoxazine
chains is one of these approaches. Fluorene contains two
benzene rings linked with a five-membered ring and pro-
vides high overlaps of p-orbitals. Polymers containing a
fluorenyl structure in their backbone (so-called Cardo-type
polymers) have many excellent improved properties, such
123
1914
as good heat-resistant, high char yield, high limited oxygen
index, good flame-retardance, and excellent solubility in
common organic solvents [18, 19]. Recently, various
researches on synthesis, polymerization behavior, curing
kinetics, and thermal properties of fluorene-based ben-
zoxazines have been reported [20, 21]. However, their
further applications were still limited mainly due to the
brittleness of the formed polymers, despite the advanta-
geous thermal properties. A numerous studies have been
conducted aiming to improve the toughness of the poly-
benzoxazine thermosets. The first one is related to the
preparation of novel benzoxazine monomers containing
aliphatic soft segments which can afford much tougher
polybenzoxazines [2224]. The second one is based on the
incorporation of some elastomeric or thermoplastic poly-
mers into the polybenzoxazine structure such as the use of
rubber [25], polyurethane [26], polysiloxane [27], poly-
sulfone [28], and poly(epsilon-caprolactone) [29] as the
toughening agent blending with benzoxazine monomers.
Moreover, main-chain type poly(benzoxazine-co-ure-
thane)s [30] and poly(benzoxazine-co-sulfones)s [31] have
been successfully synthesized to modify the brittleness of
polybenzoxazines. The telechelic polybenzoxazines with
thermoplastic oligomers as a backbone were also found to
be more efficient in improving the toughness of this kind of
thermoset [3235].
Poly(ether ketone ketone) (PEKK), as a representative of
poly(aryl ether ketone) (PAEK), is known as a high perfor-
mance engineering thermoplastic. The PAEK is used in a wide
range of fields, such as polymer films, molding resins, coating,
and insulating materials. Their excellent mechanical, electri-
cal, and chemical properties promote them to be a better
candidate for advanced materials [3638]. The incorporation
of PAEK into polybenzoxazines has been proved its capability
to overcome the brittleness of these polymers. Ishida and
coworkers successfully synthesized PAEK with benzoxazine
end groups [39]. They calculated the chain length of the oli-
gomer using 1H NMR and studied the tensile strength, the
probability of reaction, the degree of swelling, and the gel
fraction at different degree of end-capping. However, the
descriptions of the synthesis, curing behavior, and thermal
properties about fluorene-based polybenzoxazines containing
PEKK oligomers have not been reported up to now.
In the present work, novel series of fluorene-based
benzoxazine-endcapped co-PEKKs were successfully syn-
thesized from phenol-ended co-PEKKs, formaldehyde, and
n-butylamine, in which the phenol-ended co-PEKKs were
prepared with different molar ratios of 2,7-dihydroxy-9-
fluorenone to bisphenol-A. The chemical structures of the
prepared co-PEKKs and B-PEKKs were confirmed by
FTIR and 1H NMR spectroscopies. The curing behavior of
B-PEKKs and the thermal properties of the cured polymers
were investigated using DSC and TG, respectively. The
123
H. Wang et al.
dynamic mechanical properties of the prepared polymer
films were evaluated by DMA. This work aims to develop a
new approach to improve the toughness of fluorene-con-
taining polybenzoxazines without much sacrifice of their
advantageous thermal properties through incorporating of
co-PEKKs into benzoxazine backbone.
Experimental
Materials
2,7-dihydroxy-9-fluorenone (BHK) and bisphenol-A (BPA)
were obtained from Shanghai Aladdin Reagent Co., Ltd
(China). 4,40 -difluorobenzophenone was purchased from
Chengdu Xiya Reagent Co., Ltd (China). Formaldehyde
(37 mass% in water) is purchased from Tianjin fengchuan
Chemical Reagent Co., Ltd (China). All the other reagents
and solvents were purchased from Tianjin Kermel Chem-
ical Reagent Co., Ltd (China), and used without further
purification.
Synthesis of phenol-ended co-PEKKs
These phenol-ended co-PEKKs were prepared by 4,40 -
difluorobenzophenone and bisphenol compounds under the
presence of dried potassium carbonate, and the molar ratio of
4,40 -difluorobenzophenone to the mixed bisphenol com-
pounds was 2:3. The synthesis of phenol-ended co-PEKK
with a 2:1 molar ratio of BHK:BPA was chosen as a repre-
sentative example. 4,40 -difluorobenzophenone (4.36 g,
0.02 mol), 2,7-dihydroxy-9-fluorenone (4.24 g, 0.02 mol),
bisphenol-A (2.28 g, 0.01 mol), dried potassium carbonate
(4.5 g, 0.033 mol), 100 mL N, N-dimethylacetamide, and
15 mL toluene were added to a 250-mL three neck flask
equipped with a condenser, nitrogen inlet, a Dean Stark trap,
and magnetic stirrer. The mixture was first heated at 160 C
for 3 h to remove the resulting water, and then the temperature
was raised up to 170 C and kept for another 3 h to complete
the reaction. Once the reaction completed, the solution was
cooled to room temperature and filtered to remove the solid
portions. The filtered liquid was poured into distilled water
containing 1 mass% acetic acid to precipitate the oligomer.
The oligomer was then filtered and washed several times with
distilled water until neutral, followed by drying in a vacuum
oven to afford a brown powdery phenol-ended co-PEKKs,
abbreviated as PEKK21 (60 % yield, Mn = 2,135 g mol1,
Mw = 3,612 g mol1, PDI = 1.69). FT-IR (KBr, cm1):
3,6003,300 (OH stretching), 2,965 (CH stretching), 1,658,
1,718 (C=O stretching), 1,231 (COC asymmetric stretch-
ing). 1H NMR (500 MHz, CDCl3, ppm): 1.651.71 (ArC
CH3), 6.767.79 (ArH).
Synthesis, curing behavior and thermal properties of co-PEKKs
The same synthesis pathway was applied to prepare
other phenol-ended co-PEKKs: PEKK01 (57 % yield,
Mn = 2,596 g mol1, Mw = 4,201 g mol1, PDI = 1.62),
PEKK18 (57 % yield, Mn = 2,468 g mol1, Mw =
3,973 g mol1, PDI = 1.61), PEKK14 (59 % yield,
Mn = 2,384 g mol1, Mw = 3,910 g mol1, PDI = 1.64),
PEKK12 (60 % yield, Mn = 2,365 g mol1, Mw =
4,001 g mol1, PDI = 1.69), PEKK11 (60 % yield,
Mn = 2,252 g mol1, Mw = 3,693 g mol1, PDI = 1.64),
and PEKK10 (62 % yield, Mn = 1,814 g mol1, Mw =
2,918 g mol1, PDI = 1.61).
Synthesis of B-PEKKs
Formaldehyde (4.86 g, 0.06 mol) and 1,4-dioxane (10 mL)
were added to a 100-mL three neck round-bottomed flask
equipped with a magnetic stirrer and reflux condenser. The
mixture was firstly cooled below 5 C, and then the n-
butylamine (2.19 g, 0.03 mol) in 1,4-dioxane (10 mL) was
added drop-wise and reacted for 2 h. After that, the
PEKK21 (6.5 g, 0.003 mol) was added to the mixture and
reacted at 110 C for 6 h. The solution was cooled to room
temperature and poured into ethanol. The precipitate
powder was isolated by filtration and washed thoroughly
with ethanol. The obtained product was dried under vac-
uum oven to afford a brown powder B-PEKK21 (76 %
yield, Mn = 2,335 g mol1, Mw = 3,923 g mol1, PDI =
1.68). FT-IR (KBr, cm1): 1,231 (COC asymmetric
stretching), 1,160 (CNC asymmetric stretching), 1,080
(COC symmetric stretching), 928 (CH out-of-plane
bending). 1H NMR (500 MHz, CDCl3, ppm): 0.93 (CH3),
1.36, 1.54, 2.75 (CH2CH2CH2), 1.661.71 (ArCCH3), 350 C at a heating rate of 20 C min-1. The thermogravi-
3.954.02 (ArCH2N), 4.834.89 (OCH2N), 6.717.81 metric measurements were carried out by a TA Instruments
(ArH).
Similar procedure was used to synthesize other B-PEKKs,
and they are abbreviated with B-PEKK01, B-PEKK18,
B-PEKK14, B-PEKK12, B-PEKK11, and B-PEKK10,
respectively. B-PEKK01 (71 % yield), B-PEKK18 (74 %
yield), B-PEKK14 (74 % yield), B-PEKK12 (75 % yield),
B-PEKK11 (76 % yield), and B-PEKK10 (79 % yield).
Curing of B-PEKKs
All the fluorene-containing benzoxazine-endcapped co-
PEKKs were polymerized without any initiator or catalyst
according to the following schedule: 150 C/2 h, 180 C/
3 h, and 210 C/2 h under a pressure of 0.1 MPa. The
following abbreviations will be used for this series of pol-
ybenzoxazines: PB-PEKK01, PB-PEKK18, PB-PEKK14,
PB-PEKK12, PB-PEKK11, PB-PEKK21, and PB-PEKK10,
respectively.
1915
Preparation of polybenzoxazine films
Solventless method was used to prepare the polybenzox-
azine films. All the synthesized benzoxazine monomers
were melted and cast on a glass plate, and their resulting
viscous prepolymers were degassed in a vacuum oven. The
films were finally cured at 150 C for 2 h, 180 C for 3 h,
and 210 C for 2 h.
Characterization
Fourier transform infrared (FTIR) spectra were recorded by a
Perkin-Elmer Spectrum 100 spectrometer in the range of
4,000650 cm-1, which was equipped with a deuterated
triglycine sulfate (DTGS) detector and KBr optics. Trans-
mission spectra were obtained at a resolution of 4 cm-1 after
averaging two scans by casting a thin film on a KBr plate for
monomers and cured samples. 1H NMR characterizations
were performed by a Bruker AVANCE-500 NMR spec-
trometer using deuterated chloroform (CDCl3) as solvent
and tetramethylsilane (TMS) as internal standard at 25 C.
Molecular mass and polydispersities were determined by gel
permeation chromatography (GPC) equipped with a Waters
2414 refractive-index detector using tetrahydrofuran as the
eluent at a flow rate of 1 mL min1. DSC measurements were
evaluated by a TA Q200 differential scanning calorimeter
under a 50 mL min-1 constant flow of nitrogen. The
instrument was calibrated with a high-purity indium stan-
dard, and a-Al2O3 was used as the reference material. About
5 mg of sample was put into a hermetic aluminum sample
pan at 25 C, which was then sealed and tested immediately.
The dynamic scanning experiments ranged from 30 to
Q50 at a heating rate of 20 8C min-1 from 30 to 800 8C
under nitrogen atmosphere at a flow rate of 50 mL min-1.
The dynamic mechanical thermal properties of the poly-
benzoxazine films were performed by a TA Q800 dynamic
mechanical analyzer at a frequency of 1 Hz and amplitude of
10 lm.
Results and discussion
Synthesis and characterization
The synthesis of B-PEKKs was conducted in two steps. In
the first step, phenol-ended co-PEKKs were prepared by
varying the molar ratio of BHK to BPA. The average
number molecular mass of these co-PEKKs is from 1,814
to 2,596 g mol-1, and the polymerization degree of them is
from 3 to 4. In addition, the molecular mass of co-PEKKs
decreases with the increasing content of BHK. These
123
1916 H. Wang et al.

O
O CH3
mF nx HO OH n(1x)HO DMAc, Toluene
F OH
CH3 K2CO3

O O
CH3 O CH3 O O NH2
HO O C O O C O O C O OH
CH3 CH3 nx1 n(1x)1 (CH2O)n

O O
CH3 O CH3 O O
O O C O O C O O C O O
CH3 CH3 nx1 n(1x)1
N N
m/n = 2/3, 0 x 1

Scheme 1 The synthesis route of benzoxazine-endcapped co-PEKKs

results indicate that the lower content of BPA is, the con- (a) PEKK01 2965 1658
tent of hydroxyl group is higher in per unit mass. At the PEKK18
second step, these B-PEKKs were prepared by the usual
monomer synthesis reaction of phenol-ended co-PEKKs PEKK14

Transmittance/%
with n-butylamine, and formaldehyde [40]. The synthesis
PEKK12
routes of these co-PEKKs and B-PEKKs are shown in
PEKK11
Scheme 1.
PEKK21
The FTIR spectra of these co-PEKKs and B-PEKKs are
PEKK10
shown in Fig. 1a, b, respectively. As shown in Fig. 1a, the
absorption bands at 3,6003,300 cm-1 are assigned to the 1012
stretching vibration of OH group. The bands at 2,965 cm-1 925
833
1718 1158
are attributed to the asymmetric CH3 stretching vibration of 1231

bisphenol-A. The absorptions located at 1,658 cm-1 are 3600 3200 1600 1200 800
corresponded to the C=O stretching vibration [39]. Mean- Wavenumber/cm1
while, the sharp bands at 1,718 cm-1 are ascribed to the
stretching vibration of C=O attached with fluorene ring for (b) B-PEKK01
1658
BHK. The absorption peaks at 1,596, 1,502, and 1,460 cm-1
are attributed to the vibration of benzene skeleton. The B-PEKK18
B-PEKK14
strong bands at 1,231 cm-1 are due to the aromatic ether
Transmittance/%

stretching vibration, and the absorption bands at 1,158 and B-PEKK12

1,012 cm-1 are in-plane deformation bands of aromatic B-PEKK11

hydrogen. Moreover, the bisphenyl ketone band appears at B-PEKK21

925 cm-1, and the bands at 833 cm-1 are assigned to the B-PEKK10
para-substituted benzene ring [41]. Additionally, as shown
in Fig. 1b, the absorption bands located at 927928 cm-1 928~927
1080~1061
are assigned to the characteristic peaks of the benzene with 1718 1161~1159
an attached oxazine ring [42]. Also the asymmetric and 1240~1226
symmetric stretching vibrations of COC are located at 3600 3200 1600 1200 800
1,2261,240 and 1,0611,080 cm-1, respectively. And the Wavenumber/cm1
asymmetric stretching vibrations of CNC located at
1,1591,161 cm-1 [43]. The FTIR results indicate that the Fig. 1 FTIR spectra of the co-PEKKs (a) and B-PEKKs (b)
characteristic absorption bands of these two oxazine rings
have slight difference but not obviously, which is not only shift of 1.71 ppm is assigned to the methyl group resonance
attributed to the overlap of characteristic peaks for co-PE- of bisphenol-A in the main chain [39]. The signals of the
KKs and benzoxazine rings but also due to the dilution methylene protons of CH2 groups give doublets at 3.95
effect as higher PEKK content contains less number of and 4.02 ppm for ArCH2N, 4.83 and 4.89 ppm for O
benzoxazines. CH2N, in which the chemical shifts of 4.02 and 4.89 ppm
Figure 2 shows the 1H NMR spectra of these B-PEKKs. are attributed to the oxazine ring from BHK, while the
The aromatic protons are observed at 6.767.79 ppm. The chemical shifts of 3.95 and 4.83 ppm belong to the oxazine
chemical shift of 1.65 ppm is assigned to the methyl group ring from BPA. From the result of 1H NMR spectrum, there
resonance of bisphenol-A at the chain end, and the chemical exist two types of oxazine rings, one is attributed to BHK

123
Synthesis, curing behavior and thermal properties of co-PEKKs 1917

B-PEKK01 275 C

Exo
91 C (I)
20.8 J/g
B-PEKK18
118 C (I) 260 C

B-PEKK14 258 C 26.5 J/g

Heat flow/W g 1 Endo

119 C (I)
B-PEKK01 257 C
B-PEKK12 29.9 J/g
120 C (I)
B-PEKK18 246 C
B-PEKK11 32.5 J/g
B-PEKK14 133 C (I) 246 C 33.7 J/g
B-PEKK21
B-PEKK12 241 C
134 C (I) 40.4 J/g
B-PEKK10
B-PEKK11
194 C (I) 56.6 J/g
B-PEKK21

B-PEKK10
50 100 150 200 250 300

8 7 6 5 4 3 2 1 0 Temperature/C
/ppm Fig. 3 DSC curves of the benzoxazine-endcapped co-PEKKs
1
Fig. 2 H NMR spectra of the benzoxazine-endcapped co-PEKKs

Exo
and the other is assigned to BPA. Moreover, the 1H NMR 210 C
spectrum also shows that the real oxazine ring ratios of BHK 214 C (I)
to BPA for B-PEKK18, B-PEKK14, B-PEKK12,
Heat flow/W g 1 Endo

180 C
B-PEKK11, and B-PEKK21 are 2:7, 1:3, 5:8, 2:1, and 10:3,
171 C (I)
respectively, which are higher than that of their starting 4.2 J/g
150 C
ratios. For BHK, the larger steric hindrance of cardo group 140 C (I)
31.5 J/g
hinders the formation of PEKK oligomers with longer chain
B-PEKK21
segments. Consequently, the number of BPA in the chain
134 C (I) 40.4 J/g
ends is less than that of BHK in co-PEKKs, which is in
accordance with the result of GPC.

50 100 150 200 250 300

Curing behavior of these B-PEKKs
The curing behavior of the prepared B-PEKKs was studied
by DSC. Figure 3 shows the non-isothermal DSC curves of
B-PEKKs. As can clearly be seen from Fig. 3, each fluo-
rene-containing benzoxazine-endcapped co-PEKKs shows
two main thermal transitions. The stepwise decreases in
heat capacity of the samples from 91 to 196 C are the
glass transition temperatures (Tg) of the co-PEKKs back-
bones. However, the thermal transitions located at
241275 C are attributed to the thermal curing charac-
teristic of oxazine ring opening. The DSC curves indicate
that the exothermic temperatures of these B-PEKKs are
slightly higher than that of conventional fluorene-contain-
ing benzoxazine due to the dilution effect of the reactive
ring by the non-reactive co-PEKKs chain and the restricted
mobility of the oligomers [34, 39, 40]. Moreover, the
exothermic temperature decreases as the content of BHK in
B-PEKKs increases, which indicates that the oxazine ring
attached with BHK cures preferentially, and then the
Temperature/C
Fig. 4 DSC curves of B-PEKK21 at each curing stage
hydroxyl groups generated catalyze the ring-opening of the
remaining oxazine ring till the formation of the final net-
work structure. Notably, the enthalpy values for the syn-
thesized B-PEKKs are extremely lower than that of other
benzoxazines, which can be attributed that the higher
molecular mass monomer contains less number of oxazine
rings per unit mass [44].
Figure 4 illustrates the non-isothermal DSC curves of
B-PEKK21 at each curing stage. As shown in Fig. 4, the
degree of curing gradually increases with the heat treat-
ment temperature increasing, and the polymerization
reaction is almost completed at 210 C. At each curing
stage, the step changes of the curves are attributed to the Tg
values of each oligomers.

123
1918 H. Wang et al.

Table 1 Thermal properties of the cured polymers

Sample Tg/oCa Tg/oCb E/ T5/oC Char yield at
code MPac 800 C/%

PBPEKK01 167 178 2,038 427 38

PBPEKK18 179 188 2,039 426 49
PBPEKK14 186 191 2,121 424 52
PBPEKK12 196 214 2,212 414 53
PBPEKK11 201 227 2,591 413 58
PBPEKK21 214 401 60
PBPEKK10 256 363 64
a
The Tg values were measured by DSC
b
The Tg values were examined by DMA
c
E, The storage modulus were recorded at 50 C

300
B-PEKK01 Fig. 6 Photographs of thin films: a PB-PEKK01, b PB-PEKK18,
280 B-PEKK18
c PB-PEKK14, d PB-PEKK12, and e PB-PEKK11
B-PEKK14
260
B-PEKK12
240 B-PEKK11
B-PEKK21 BHK increases. These results are mainly attributed to the
220 B-PEKK10 higher rigidity of fluorene skeleton in the chain backbone,
which restrains the internal rotations and thermal motion of
Tg/C

200
180
160
140
120
100
150 160 170 180 190
Temperature/C
Fig. 5 Variation of Tg versus temperature by DSC
Glass transition temperature of these PB-PEKKs
The Tg values of these PB-PEKKs obtained by DSC and
DMA are summarized in Table 1. The Tg values of the
prepared oligomers at different curing stages are depicted
in Fig. 5, which increase with the increasing of heat
treatment temperature, and the Tg values reach the maxi-
mum as the formation of infinite network structure. As also
can be seen in Fig. 5, as the content of BHK increases, the
Tg values of the oligomers increase. In addition, it can be
clearly seen that the Tg value of PB-PEKK01 is the lowest
one in this series of polymers, but still remains much
higher than that of typical bisphenol-A-n-butylamine-based
polybenzoxazine (135 C) [45]. However, the Tg value of
PB-PEKK10 is the highest one, which is 41 C higher than
that of traditional fluorene-n-butylamine-based poly-
benzoxazine [40].
Also it appears that the Tg values of these crosslinked
polymers shift to higher temperatures as the content of
polymer segments [46].
Film forming and mechanical properties of PB-PEKKs
These films were prepared by solventless method, and the
flexibility of these PB-PEKK films was also demonstrated. It
should be pointed out that the films with higher BHK con-
200 210
tent (PB-PEKK10 and PB-PEKK21) were too brittle to form
their casting successfully. The photographs of PB-PEKK01,
PB-PEKK18, PB-PEKK14, PB-PEKK12, and PB-PEKK11
are shown in Fig. 6. It is seen that PB-PEKK01 and PB-
PEKK18 are completely bendable without any difficulty.
Dynamic mechanical properties of the cured films were
examined by DMA. Figure 7a, b shows the temperature
dependency of the storage modulus (E) and tan d for PB-
PEKK01, PB-PEKK18, PB-PEKK14, PB-PEKK12, and PB-
PEKK11, respectively. It is observed that the storage mod-
ulus maintains at lower value by increasing the BPA con-
tent, indicating the improvement in the toughness of these
polymers. It has been reported that the brittleness may arise
from the high rigidity of the chain itself [39]. Therefore, the
introduction of fluorenyl group increased the stiffness of
these polymers, but the fluorene-containing polybenzoxa-
zines based on co-PEKKs still exhibit a significantly
improved toughness comparing to the typical bisphenol-A
and the fluorene-based polybenzoxazine [47, 48].
As can be seen from Fig. 7b, the peak values of tan d,
associated with the Tg values of these PB-PEKKs, shift to
higher temperatures as the content of BHK rises, which is
in accordance with the previous DSC results.

123
Synthesis, curing behavior and thermal properties of co-PEKKs 1919

(a) 3000 (a) a PB-PEKK01

a PB-PEKK01 100
b PB-PEKK18 b PB-PEKK18
c PB-PEKK14
2500 c PB-PEKK14
90 d PB-PEKK12
d PB-PEKK12
Storage modulus/MPa

e PB-PEKK11
e PB-PEKK11
f PB-PEKK21
2000 80 g PB-PEKK10

Mass/%
1500 70 g
f
60 e
1000 d
a b c d e
c
50 b
500
a
40
0
50 100 150 200 250 100 200 300 400 500 600 700 800
Temperature/C Temperature/C

(b) 1.8 (b) a PB-PEKK01

a PB-PEKK01 a
1.0 b PB-PEKK18
1.6 b PB-PEKK18
c PB-PEKK14
a b c PB-PEKK14
1.4 d PB-PEKK12
d PB-PEKK12
0.8 e PB-PEKK11

Deriv. mass % C1
1.2
c e e PB-PEKK11 f PB-PEKK21
d g PB-PEKK10
1.0 0.6 b
Tan

0.8 c
0.4 d
0.6
e
0.4 f
0.2 g
0.2

0.0 0.0
100 150 200 250 100 200 300 400 500 600 700 800
Temperature/C Temperature/C

Fig. 7 Temperature dependence curves of storage modulus (a) and
tan d (b) for PB-PEKK01, PB-PEKK18, PB-PEKK14, PB-PEKK12,
and PB-PEKK11
Thermal stabilities of the prepared PB-PEKKs
The thermal stabilities of these PB-PEKKs were evaluated
by TG under nitrogen atmosphere. The TG and DTG
curves of them at various compositions are shown in
Fig. 8a, b, respectively. The values of 5 % mass loss
temperatures (T5) as well as the char yield (Yc) at 800 C
are collected in Table 1. The results clearly indicate that
two main processes occur during the thermal degradation
of co-PEKKs functional polybenzoxazines. The first deg-
radation below 400 C is due to the volatilization of amine
fragments from the benzoxazine rings at the chain end,
whereas the second degradation between 400 and 600 C is
related to the decomposition of both polybenzoxazines and
co-PEKKs [39, 49, 50]. Moreover, as the content of BHK
rises, the volatilization of amine fragments increases, but
the degradation of polybenzoxazines and co-PEKKs
decreases. This is due to the higher content of BHK in the
Fig. 8 TG (a) and DTG (b) curves of these cured polymers
polymers shortens the length of co-PEKK chain segments,
thus the number of benzoxazine at the chain end would be
much higher. In addition, the T5 values of all the synthe-
sized polymers are above 360 C, which are much higher
than that of the traditional fluorene-containing and the bi-
sphenol-A-based polybenzoxazines, abbreviated as poly(B-
bbf) (329 C) and PB-a (310 C) [16, 51], respectively.
Furthermore, it appears that the char yields of the prepared
PB-PEKKs increase with the increasing of BHK content in
these polymers. It is worthy to note that the char yields of
PB-PEKK21 and PB-PEKK10 exceed 60 %, which are
extremely higher than those of traditional polybenzoxa-
zines and PAEKs [52].
Conclusions
Several fluorene-based benzoxazine-endcapped co-
poly(ether ketone ketone)s with different molar ratios of

123
1920
2,7-dihydroxy-9-fluorenone to bisphenol-A were success-
fully synthesized and characterized. The produced oligo-
mers were further crosslinked through the thermal
activated ring-opening polymerization of the benzoxazine
rings to form the cured network structure. The results
indicate that the molecular mass of co-PEKKs decreases
with increasing the content of BHK. The thermal stabilities
of the obtained thermosets are better than those of typical
fluorene-containing and bisphenol-A-based polybenzoxa-
zines. In addition, the obtained thermosets exhibit a higher
glass transition temperature (Tg) and still maintain at better
toughness. Also, as the content of BHK in co-PEKKs
increases, both the Tg values and the char yields of the
synthesized polymers are enhanced, while their T5 values
relatively decrease.
Acknowledgements The authors greatly appreciated the financial
supports from National Natural Science Foundation of China (Project
Nos 50973022), Specialized Research Funds for the Doctoral Pro-
gram of Higher Education (Project No. 20122304110019), Funda-
mental Research Funds for the Central Universities (Project Nos.
HEUCFT1009 and HEUCF201310006), and the open fund of Key
Laboratory of Superlight Material and Surface Technology of Min-
istry of Education, Harbin Engineering University.
References
1. Ishida H, Agag T. Handbook of benzoxazine resins. Oxford:
Elsevier; 2011.
2. Ghosh NN, Kiskan B, Yagci Y. Polybenzoxazinesnew high
performance thermosetting resins: synthesis and properties. Prog
Polym Sci. 2007;32(11):134491.
3. Yagci Y, Kiskan B, Ghosh NN. Recent advancement on poly-
benzoxazine-a newly developed high performance thermoset.
J Polym Sci Part A. 2009;47(21):556576.
4. Zhao P, Zhou Q, Deng Y, Zhu R, Gu Y. A novel benzoxazine/
epoxy blend with multiphase structure. RSC Adv. 2014;4(1):
23842.
5. Chiou K, Hollanger E, Agag T, Ishida H. Highly improved
thermal properties of hydroxyl-containing polymers via modifi-
cation by benzoxazine groups. Macromol Chem Phys. 2013;214
(14):162935.
6. Zuniga C, Larrechi MS, Lligadas G, Ronda JC, Galia M, Cadiz V.
Phosphorus flame retardant polybenzoxazine foams based on renew-
able diphenolic acid. Polym Degrad Stab. 2013;98(12):261726.
7. Li SF, Tao M. Preparation and properties of copolymer resins
based on phenolphthalein benzoxazine-benzoic acid and bisox-
azoline. J Therm Anal Calorim. 2013;113(2):6339.
8. Wang J, Wang H, Liu JT, Liu WB, Shen XD. Synthesis, curing
kinetics and thermal properties of novel difunctional chiral and
achiral benzoxazines with double chiral centers. J Therm Anal
Calorim. 2013;114(3):125564.
9. Liu Y, Liao C, Hao Z, Luo X, Jing S, Run M. The polymerization
behavior and thermal properties of benzoxazine based on o-
allylphenol and 4,40 -diaminodiphenyl methane. React Funct
Polym. 2014;75:915.
10. Liu YF, Zhang HL, Wang M, Liao CY, Zhang J. Thermal deg-
radation behavior and mechanism of polybenzoxazine based on
bisphenol-S and methylamine. J Therm Anal Calorim. 2013;
112(3):12139.
123
H. Wang et al.
11. Liu YF, Li ZH, Zhang J, Zhang HL, Fan HY, Run MT. Polymerization
behavior and thermal properties of benzoxazine based on 4,4-diam-
inodiphenyl ether. J Therm Anal Calorim. 2013;111(2):152330.
12. Lochab B, Varma IK, Bijwe J. Cardanol-based bisbenzoxazines
effect of structure on thermal behaviour. J Therm Anal Calorim.
2012;107(2):6618.
13. Li S, Yan S, Yu J, Yu B. Synthesis and characterization of new ben-
zoxazine-based phenolic resins from renewable resources and the
properties of their polymers. J Appl Polym Sci. 2011;122(5):28438.
14. Li X, Xia Y, Xu W, Ran Q, Gu Y. The curing procedure for a
benzoxazinecyanateepoxy system and the properties of the
terpolymer. Polym Chem. 2012;3(6):162933.
15. Chutayothin P, Ishida H. Cationic ring-opening polymerization of
1,3-benzoxazines: mechanistic study using model compounds.
Macromolecules. 2010;43(10):456272.
16. Wang J, Wu MQ, Liu WB, Yang SW, Bai JW, Ding QQ, et al.
Synthesis, curing behavior and thermal properties of fluorene
containing benzoxazines. Eur Polym J. 2010;46(5):102431.
17. Santhosh Kumar KS, Reghunadhan Nair CP, Ninan KN. Rhe-
okinetic investigations on the thermal polymerization of ben-
zoxazine monomer. Thermochim Acta. 2006;441(2):1505.
18. Hsiao SH, Li CT. Synthesis and characterization of new fluorene-based
poly(ether imide)s. J Polym Sci Part A. 1999;37(10):140312.
19. Liu W, Qiu Q, Wang J, Huo Z, Sun H. Curing kinetics and
properties of epoxy resinfluorenyl diamine systems. Polymer.
2008;49(20):4399405.
20. Wang J, Fang X, Wu MQ, He XY, Liu WB, Shen XD. Synthesis,
curing kinetics and thermal properties of bisphenol-AP-based
benzoxazine. Eur Polym J. 2011;47(11):215868.
21. Wang J, He XY, Liu JT, Liu WB, Yang L. Investigation of the
polymerization behavior and regioselectivity of fluorene diamine-
based benzoxazines. Macromol Chem Phys. 2013;214(5):61728.
22. Agag T, Akelah A, Rehab A, Mostafa S. Flexible polybenzox-
azine thermosets containing pendent aliphatic chains. Polym Int.
2012;61(1):1248.
23. He XY, Wang J, Ramdani N, Liu WB, Liu LJ, Yang L. Inves-
tigation of synthesis, thermal properties and curing kinetics of
fluorene diamine-based benzoxazine by using two curing kinetic
methods. Thermochim Acta. 2013;564(20):518.
24. He XY, Wang J, Wang YD, Liu CJ, Liu WB, Yang L. Synthesis,
thermal properties and curing kinetics of fluorene diamine-based
benzoxazine containing ester groups. Eur Polym J.
2013;49(9):275968.
25. Ishida H, Chaisuwan T. Mechanical property improvement of
carbon fiber reinforced polybenzoxazine by rubber interlayer.
Polym Compos. 2003;24(5):597607.
26. Takeichi T, Guo Y, Agag T. Synthesis and characterization of
poly(urethane-benzoxazine) films as novel type of polyurethane/phe-
nolic resin composites. J Polym Sci Part A. 2000;38(22):416576.
27. Bagherifam S, Kiskan B, Aydogan B, Yagci Y, Hacaloglu J.
Thermal degradation of polysiloxane and polyetherester con-
taining benzoxazine moieties in the main chain. J Anal Appl
Pyrolysis. 2011;90(2):15563.
28. Xia Y, Yang P, Zhu R, Zhang C, Gu Y. Blends of 4,40 -diamin-
odiphenyl methane-based benzoxazine and polysulfone: mor-
phologies and properties. J Polym Res. 2014;21(3):387.
29. Huang JM, Yang SJ. Studying the miscibility and thermal
behavior of polybenzoxazine/poly(e-caprolactone) blends using
DSC, DMA, and solid state 13C NMR spectroscopy. Polymer.
2005;46(19):806878.
30. Baqar M, Agag T, Ishida H, Qutubuddin S. Poly(benzoxazine-co-
urethane)s: a new concept for phenolic/urethane copolymers via
one-pot method. Polymer. 2011;52(2):30717.
31. Altinkok C, Kiskan B, Yagci Y. Synthesis and characterization of
sulfone containing main chain oligobenzoxazine precursors.
J Polym Sci Part A. 2011;49(11):244550.
Synthesis, curing behavior and thermal properties of co-PEKKs
32. Qi H, Pan G, Zhuang Y, Huang F, Du L. Synthesis and character-
ization of acetylene-terminated polybenzoxazines based on poly-
aralkyl-phenolic prepolymer. Polym Eng Sci. 2010;50(9):17517.
33. Kiskan B, Colak D, Muftuoglu AE, Cianga I, Yagci Y. Synthesis
and characterization of thermally curable benzoxazine-functio-
nalized polystyrene macromonomers. Macromol Rapid Commun.
2005;26(10):81924.
34. Ates S, Dizman C, Aydogan B, Kiskan B, Torun L, Yagci Y. Syn-
thesis, characterization and thermally activated curing of polysulf-
ones with benzoxazine end groups. Polymer. 2011;52(7):15049.
35. Biju R, Nair CPR, Gouri C, Ninan KN. Rheokinetic cure charac-
terization of epoxy-anhydride polymer system with shape memory
characteristics. J Therm Anal Calorim. 2012;107(2):693702.
36. Jinhuan L, Young ML. Synthesis and characterization of highly
soluble poly(aryl ether ketone-benzoxazole) copolymers with
hexafluoroisopropylidene moieties by direct copolymerization.
Macromol Chem Phys. 2006;207(20):18807.
37. Gao Y, Jian X, Xuan Y, Xiang S, Liang P, Guiver MD. Synthesis
and characterization of soluble copoly(ether ketone)s containing
double bonds. J Polym Sci Part A. 2002;40(20):344954.
38. Shen K, Pang J, Feng S, Wang Y, Jiang Z. Synthesis and prop-
erties of a novel poly(aryl ether ketone)s with quaternary
ammonium pendant groups for anion exchange membranes.
J Membr Sci. 2013;440:208.
39. Nakamura M, Ishida H. Synthesis and properties of new cros-
slinkable telechelics with benzoxazine moiety at the chain end.
Polymer. 2009;50(12):268895.
40. Wang J, Ren TT, Wang YD, He XY, Liu WB, Shen XD. Syn-
thesis, curing behavior and thermal properties of fluorene-con-
taining benzoxazines based on linear and branched butylamines.
React Funct Polym. 2014;74:2230.
41. Al Lafi AG. FTIR spectroscopic analysis of ion irradiated poly
(ether ether ketone). Polym Degrad Stab. 2014;105:12233.
1921
42. Agag T, Jin L, Ishida H. A new synthetic approach for difficult
benzoxazines: preparation and polymerization of 4,40 -diamin-
odiphenyl sulfone-based benzoxazine monomer. Polymer. 2009;
50(25):59404.
43. Dunkers J, Ishida H. Vibrational assignments of 3-alkyl-3,4-
dihydro-6-methyl-2H-1,3-benzoxazine in the fingerprint region.
Spectrochim Acta. 1995;51A(6):106174.
44. Yildirim A, Kiskan B, Demirel AL, Yagci Y. Synthesis, character-
ization and properties of naphthoxazine-functional poly(propylene-
oxide)s. Eur Polym J. 2006;42(11):300614.
45. Ishida H, Low HY. A study on the volumetric expansion of benzox-
azine-based phenolic resin. Macromolecules. 1997;30(4):1099106.
46. Fukuda M, Sawada K, Yoshino K. Synthesis of fusible and sol-
uble conducting polyfluorene derivatives and their characteristics.
J Polym Sci Part A. 1993;31(10):246572.
47. Takeichi T, Kawauchi T, Agag T. High performance poly-
benzoxazines as a novel type of phenolic resin. Polym J.
2008;40(12):112131.
48. Ishida H, Allen DJ. Mechanical characterization of copolymers
based on benzoxazine and epoxy. Polymer. 1996;37(20):448795.
49. Niu Y, Zhu X, Liu L, Zhang Y, Wang G, Jiang Z. Synthesis and
characterization of poly(aryl ether ketone) with trifluoromethyl-
substituted benzene in the side chain. React Funct Polym.
2006;66(5):55966.
50. Low HY, Ishida H. Mechanistic study on the thermal decompo-
sition of polybenzoxazines: effects of aliphatic amines. J Polym
Sci Part B. 1998;36(11):193546.
51. Agag T, Takeichi T. Synthesis and characterization of novel
benzoxazine monomers containing allyl groups and their high
performance thermosets. Macromolecules. 2003;36(16):60107.
52. Wu T, Liu P, Shi M, Lu J, Ye G, Xu J. Novel copoly(ether ether
ketone)s with pendant phenyl groups: synthesis and character-
ization. Polym Int. 2011;60(9):131823.
123