Article

High Performance Polymers

1–6
Preparation and thermal stability ª The Author(s) 2016
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DOI: 10.1177/0954008316644971
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constructed by multiple heat-resistant
compositions containing boron
and silicon

Fengyi Wang, Zhixiong Huang, Guangwu Zhang

and Yunxia Li

Abstract
This work reports a boron- and silicon-containing phenolic-formaldehyde (PF) resin exhibiting an extremely high thermal
decomposition temperature and char yield and formed by copolymerizing phenol, formaldehyde, boric acid (BA), and
phenyltriethoxysilane (PTES). The structure of BA and PTES-modified PF (BSPF) resin was characterized by Fourier
transform infrared spectroscopy. Thermal stability of the investigated composites was estimated by means of thermo-
gravimetric analysis (TGA). The results of TGA indicated that the modified resin exhibited excellent thermal stability.
Specifically, the thermoset had a char yield of 77.0% when the boron and silicon contents were only 1.27 wt% and 1.7 wt%,
respectively. Compared with the unmodified resin (PF), the temperature at the maximum decomposing rate of the BSPF
increased by 84 C and its charring yield was enhanced by 15.0%. The cured products of PF and BSPF were further
investigated by X-ray diffraction and Raman spectroscopy, respectively. The incorporation of boron and silicon into the
carbon lattice results in a decrease of interlayer spacing, and Raman ID/IG values for PF and BSPF (2.63 and 1.32) show that
the rearrangement of crystalline structure leads to an increase in graphite structure and a decrease in disordered
structure upon the modification processes.

Keywords
Phenolic, boric acid, phenyltriethoxysilane, thermal stability, structure

Introduction reported in the literature. It is generally believed that the

formation of borate linkage decreased the possibility of
Phenol-formaldehyde (PF) resin is an excellent thermoset- forming ether linkage, thus the thermal resistance of the
ting resin with good mechanical properties and heat resis-
BPF improved extremely.14,15 In addition, the merit of
tance, and it has been used as matrix for thermal insulation,
organic silicone is their attractive integrated properties
flame-retardant, and ablative materials.1–3. However, the
including thermal stability,16,17 flame retardancy,18 tough-
rapid growth of PF applications has promoted extensive
ness,19 and moisture resistance.20 It is of great interest to
research to improve its heat resistance and mechanical
introduce silicone into organic polymers21–25 to endow the
properties, especially high-temperature ablation and char-
hybrids with excellent properties from both components.
ring yield. One approach is related to the incorporation of
various elements or functional groups into the backbone of
phenolic resin, such as boron, phosphorus, silicon, molyb-
denum, zirconium compounds, phenyl–phenol, and so School of material science and engineering, Wuhan University of
on.4–10 Of these, the boric acid-modified PF (BPF) exhib- Technology, Wuhan, China
ited excellent thermal properties.11 Gao et al. conducted
Corresponding author:
some seminal work on the preparation of BPF by using Fengyi Wang, School of material science and engineering, Wuhan
boric acid (BA) as boron source.12–13 A valuable explana- University of Technology, Luoshi Road No.122, 430070 Wuhan, China.
tion for the excellent thermal resistance of BPF has been Email: tswxwfy@163.com

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2 High Performance Polymers

OH OH

CH 2OH
CH 2 O

OH OC 2H 5
OH

CH 2 OH B H 5 C 2O Si OC 2H 5
HO OH

OH

B
O O
H2 H2
C C
CH 2 CH 2 CH 2 O

O B
R
O O
H 5C 2 O Si O Si O OH

R O

R C 6H 5

Figure 1. Synthesis route of BSPF. BSPF: boron and silicon-modified phenolic-formaldehyde resin.

Many studies proved that silicon is an effective component
in improving the antioxidation properties of poly-
mers.17,22,25,26 K. Haraguchi and coworkers26,27 prepared
phenolic/silica hybrid by in situ polymerization of silicon
alkoxide, and both mechanical and thermal properties were
enhanced. Silicone and phenolic resin were incompatible,
and phase separation would always occur in the
hybrids.17,28,29 The phase structure (including dispersion
state,30 particle size,19,31 and interface of the phases26)
would affect the properties of the hybrids. Structural mod-
ification of phenolics results in high thermal stability
and high carbon yield values upon pyrolysis in nitrogen
(thermogravimetric analysis (TGA)). Incorporation of
boron and phosphorous moieties25–29 and inorganic modi-
fiers30,31 into the phenolic structures are some important
examples of structural modification methods.
Despite BA and organic silicone having been relatively
well established as versatile building blocks in both supra-
molecular polymer chemistry and synthetic chemistry, to
the best of our knowledge, little attempts have been made
to combine both BA and silicone with PFs, which may
provide high-performance functional polymer materials.
Moreover, the synergistic effect of boron and silicon ele-
ment on the properties of PF, especially on the thermal
resistance and phase structure, has not been further studied.
With this aim in mind, our present work intends to intro-
duce boron and silicon structure into PFs as an effective
means of improving their heat resistance. In presented
study, a thermal-resistant boron and silicon-modified PF
(BSPF) resin was prepared by copolymerizing phenol, for-
maldehyde, BA, and phenyltriethoxysilane (PTES). The
structure of BSPF was characterized by Fourier transform
infrared (FTIR) spectroscopy. Thermal stability of the
investigated composites was estimated by means of TGA
and derivative thermal gravimetric (DTG). The structure of
cured PF and BSPF was also analyzed by X-ray diffraction
and Raman spectroscopy, respectively.
Experimental
Materials
Phenol, 37% aqueous formalin, BA, hydrochloric acid
(HCl), sodium hydroxide (NaOH), acetone, and ethanol
were all of analytical grade and were supplied by Sino-
pharm Chemical Reagent Co., Ltd (China). PTES and hex-
amethylenetetramine were purchased from Aladdin
chemicals Co., Ltd (China). All the above chemicals were
used as received.
Preparation of the BSPF
The BSPF was synthesized as presented in Figure 1. In
the mole ratio, phenol: formaldehyde: BA: PTES ¼
1:1.2:0.2:0.1. Phenol, formalin, and NaOH were added into
a four-necked flask equipped with a stirrer, a thermometer,
and a condenser. The mixture was stirred to be a homoge-
neous solution and reacted at 70 C for 1–1.5 h. Thereafter,

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Wang et al. 3

the water was removed under vacuum. In the second step,

an inorganic hybrid solution which was prepared by dissol- Si-O
BSPF
ving BA, PTES, and HCl in ethanol was added into the Si-C
B-C
solution and reaction continued at refluxing temperature
PF
for 1–2 h. After removing water through vacuum distilla-
tion, a red–brown semiliquid product BSPF was obtained.
B-O-C
Changing molar ratio of phenol and PTES can yield phe-
nolic resin with silicon content from 0% to 5%. TGA shows
that BSPF with 1.7 wt% silicon content has highest char-
ring yield, so in the following research, the BSPF is just
referred to this type of resin. The ordinary PF resin was
prepared with conventional method32 for comparison. 4000 3500 3000 2500 2000 1500 1000
To eliminate the effect of residual reactants, on the test Wave numbers (cm–1)
results of obtained BSPF resin, BSPF was purified by the
following steps. Firstly, the BSPF was added into dilute Figure 2. FTIR spectra of ordinary phenolic resin and boron and
NaOH solution and then washed the resulting precipitate silicon modified phenolic resin. FTIR: Fourier transform infrared.
with deionized water for three to four times. Finally, the
precipitate was removed by sedimentation in the centrifuge Table 1. Characteristic absorption peak of BSPF.
using deionized water as a solvent. After having repeated
The peak of
these steps for three times, the final product was dried in absorption
vacuum oven for 3 h at 65 C. Thus, the purified BSPF after band (cm1) Chemical bond
curing process was used as the sample in the following
characterization. 3410 –OH stretching of phenolic ring
2924 Stretching of –CH2–
1612, 1595, 1511 C¼C stretching of phenolic ring
Testing and characterization 1454 Scissoring vibration of –CH2–
1384 Stretching of B–O
FTIR spectra were obtained using a Nicolet 6700 infrared 1225 Stretching of CH2–O–CH2
spectrometer (Thermofisher Scientific, Waltham, Massa- 1100 C–H stretching of phenolic ring
chusetts, USA). The powdered samples were thoroughly 1056 Vibration of Si–O
mixed with potassium bromide and then pressed into pel- 968 Vibration of Si–C
lets. TGA was performed using NETZSCH STA449F3 887 C–H flexural of phenolic ring meta position
(Germany) at a heating rate of 10 C min1 under nitrogen 814 C–H flexural of phenolic ring para position
atmosphere from 50 C to 800 C. The structure of cured PF 754 C–H flexural of phenolic ring ortho position
651 Stretch vibration of B–C
and BSPF was further studied by using X-ray diffraction
and Raman spectroscopy. X-ray diffraction spectra of cured BSPF: boron and silicon-modified phenolic-formaldehyde resin.
products were obtained using a D8 Advance X-ray diffract-
ometer with copper K radiation and a nickel filter. The phenolic hydroxyl and methylol groups of PF. While com-
Raman spectra were collected from 700 to 1800 cm1 using pared with the curve of PF, the phenol hydroxyl stretch at
a Renishaw inVia Reflex system at an excitation wave- 1225 cm1 of the cured BSPF almost disappeared, and the
length of 514.5 nm. new absorption peaks at 1384 and 651 cm1 were assigned
to the B–O and B–C stretch vibrations, respectively.33
Moreover, the band at 1056 and 968 cm1 was assigned
Results and discussion to be the vibration of Si–O–Si and Si–O–ph.22 As the effect
A comparison of the IR spectra of ordinary phenolic resin of residual reactants has been eliminated, the appearance of
(PF) and BSPF is shown in Figure 2. The characteristic new absorptions peak was believed to be caused by the
absorption peaks of BSPF are shown in Table 1.The main boron and silicon phases introduced into the reaction prod-
absorption peaks of BSPF can be assigned as follows: uct. Based on the analysis above, it can be concluded that
3410 cm1: C–OH, 2924 cm1: C–H, 1384 cm1: B–O, BA and PTES have been incorporated into the reaction prod-
and 1225 cm1: CH2–O–CH2. Besides, the sharp peaks at uct and mainly exist in the form of B–O and Si–O bond.
1454 and 1595 cm1 indicated the existence of C¼C Thermal stability of the cured BSPF was assessed by
groups in benzene ring, the peaks at 2924, 1612, and TGA under nitrogen atmospheres. TGA curves of the BSPF
1511 cm1 confirmed the presence of C–H groups in ben- thermosets are presented in Figure 3. The DTG profiles are
zene ring and peaks at 887, 814, and 754 cm1 could be shown in Figure 4.
assigned to C–H flexural vibration of benzene rings. Bor- The TGA indicated that the cured BSPF possessed a
onates can be formed by the reaction of B–OH with high thermal decomposition temperature and char yield

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4 High Performance Polymers

this course were attributed to the breakage and redistribution

100
reactions of the B–O, Si–O, and C–C bonds. The incorpora-
tion of BA and PTES improved the char yield obviously, and
90 the final charring yield of the sample after pyrolysis
BSPF
increased from 62.0% to 77.0%, which was beneficial to
80 improve the integrity structure and the bonding strength of
weight (%)

the adhesive at high temperature. From the DTG curves

70 (shown in Figure 4), it can be clearly seen that the decom-
PF position peak temperature (Td,max) of BSPF was higher and
60
the decomposition rate was lower, suggesting that BA and
silane grafted on phenolic could effectively protect the
matrix from degradation. The three-dimensional network
50
structure improves the degree of branching of modified phe-
100 200 300 400 500 600 700 800
nolic resin, suggesting that the char residues of PF thermo-
Tempareture (°C)
sets with multiple heat-resistant functional groups were
more thermal stable than that of the neat phenolic resin
Figure 3. TG curves of ordinary PF and BSPF in nitrogen. system. The thermal decomposition temperatures of the
TG: thermogravimetric; PF: phenolic-formaldehyde; BSPF: boron modified composites shifted toward higher temperature
and silicon-modified phenolic-formaldehyde resin. region compared with that of the pure composite, confirming
the enhancement of thermal stability of the composites.
Raman spectroscopy is also a useful tool for obtaining
0.0 information on microstructural change in carbonaceous
materials, particularly to obtain ordered and disordered
–0.5 structural information of graphitic carbons. The D-band
(breathing mode of A1g symmetry, nearly 1358 cm1) is
mainly associated with disordered carbon and amorphous
DTG (%/min)

–1.0
–1.5
–2.0
PF
–2.5
100 200 300 400 500
Temperature (°C)
Figure 4. DTG curves of ordinary PF and BSPF in nitrogen.
DTG: derivative thermogravimetric; PF: phenolic-formaldehyde;
BSPF: boron and silicon-modified phenolic-formaldehyde resin.
(Figure 3), which demonstrated the effect of introducing the
boron and alkoxysilane structures had on the thermal stabi-
lity of PF. As can be seen from Figure 3, the weight loss of
BSPF under nitrogen atmosphere took place in three steps.
Below 300 C, the pyrolysis processes of cured PF and BSPF
are similarly, in both of which three major reaction regions
exist. In the first region, evolution of water, cross-linked by-
products and unreacted oligomers, is the main reaction.34
The initial decomposition temperature of both PF and BSPF
is about 300 C. In the range of 300–600 C, significant mass
changes were observed due to the dehydrogenation and
decomposition reactions that generated a large number of
gaseous volatile, including CO, H2O, small molecule hydro-
carbons, and so on. In the range of 600–800 C, weight loss
curve became relatively flatter. The changes observed during
carbon and the G-band (in-plane bond stretching, nearly
BSPF
1580 cm1) is derived from the C–C-stretching mode due
to the tangential vibration of carbon.35 The relationship
between the D-band and the G-band intensities should be
proportional to the degree of structural order with respect to
the graphite structure. This relationship has been largely
used in the literature in different forms, such as ID/IG.36
The ID/IG intensity ratios reflect the disorder. The micro-
600 700 800 crystalline planar size (La), which corresponds to the in-
plane dimension of the single microcrystalline domain in
carbonized products, can be determined from the integrated
intensity ratio ID/IG as follows2:
La ¼ 4:35IG =ID
The Raman spectra measured for the PF and BSPF are
shown in Figure 5. Compared with that of PF, the value ID/IG
of BSPF decreased from 2.63 to 1.32. The crystal size La of
BSPF is 3.29 nm, much larger than that of PF (1.65 nm). The
changes in the Raman spectra of PF demonstrate that the
rearrangement of crystalline structure leads to an increase in
graphite structure and a decrease in disordered structure after
introducing boron and silicon into the backbone of the resin.
The results indicated that the presence of boron or silicon
atom in the network did not disrupt the formation of gra-
phene sheet and was able to promote graphitization of PF.
The thermal properties of hybrids may also be attributed to
the formation of more orderly carbon structure.37
Evaluation of graphene structure upon the modification
processes was carried out using XRD patterns. The XRD

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Wang et al.
Intensity
PF
BSPF
800 1000 1200 1400
Wave number (cm–1)
Figure 5. Raman spectra of cured PF and cured BSPF. PF:
phenolic-formaldehyde; BSPF: boron and silicon-modified
phenolic-formaldehyde resin.
20.0
27.9
19.5
10 20 30 40 50 60
2θ/(deg)
Figure 6. XRD patterns of cured PF and BSPF samples. XRD:
X-ray diffraction; PF: phenolic-formaldehyde; BSPF: boron and
silicon-modified phenolic-formaldehyde resin.
patterns of both cured products are exhibited in Figure 6.
The appearance of a large hump around 2 ¼ 15–30 was
typical of amorphous diffraction peaks confirming the pres-
ence of an amorphous phase in the pyrolysis product.
Meanwhile, the XRD pattern of cured BSPF showed a
crystalline diffraction peak from boron trioxide at 2 ¼
27.9 . In addition, there is not any peak related to PF in
the diffraction pattern of BSPF, which clearly shows that
layers are disordered during the modification processes.
As calculated from Bragg’s law, the interlayer spacing
(d-spacing) of the cured PR is approximately 0.4665 nm,
which is larger than that of pristine graphite (d ¼ 0.3354
nm), while the cured BSPF results in a d-spacing of 0.4434
nm. The decrease in the d-spacing may be due to the crys-
talline improvement resulting from the addition of boron
and silicon and the decrease in electron density due to the
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5
boron and silicon substitution. Taking the FTIR analysis
shown in Figure 2 into consideration (1384 and 1056 cm1
correspond to B–O and Si–O characteristic absorption
peak), the cured products suggest an almost thorough poly-
condensation reaction among the reactants.
Conclusion
A kind of BSPF was successfully synthesized by using
phenol, formaldehyde, BA, PTES, ethanol, HCl, and NaOH
as raw materials. Successful modification of PF by BA and
PTES moieties was confirmed by FTIR bands of B–O and
1600 1800 Si–O stretching. Thermal behavior of the products was
investigated by TGA and DTG. The temperature at the
maximum decomposing rate of the BSPF is 520 C, 84 C
higher than that of the unmodified ones. Moreover, the
charring yield of BSPF is 77.0%, 15.0% higher than that
of PF. The structure of cured PF and BSPF was studied
using X-ray diffraction and Raman spectroscopy. The
incorporation of boron and silicon into the carbon lattice
results in a decrease in interlayer spacing. The degree of
graphitization in the PF improved due to the boron and
silicon incorporation, and Raman ID/IG values for PF and
BSPF (2.63 and 1.32) show that the presence of boron or
silicon atom in the network was able to promote graphiti-
zation of PF upon the modification processes. The formed
BSPF boronates and silicates blocked parts of phenolic hydroxyl
groups and shortened the distances among the benzene
PF
rings linking to the central boron or silicon atom compared
with PF, which was conducive to the char formation.
Declaration of Conflicting Interests
The author(s) declared no potential conflicts of interest with
70 80
respect to the research, authorship, and/or publication of this
article.
Funding
The author(s) received no financial support for the research,
authorship, and/or publication of this article.
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