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High Performance Polymers

1–11
Improving the Thermal and Mechanical ª The Author(s) 2020
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Properties of Phenolic Fiber over Boron sagepub.com/journals-permissions

DOI: 10.1177/0954008320976754
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Modified High-Ortho Phenolic Resin

Yu Ren1,2,3 , Xu Lin1,2,3, Zhengjun Shi2,3, Yunwu Zheng2,3,

Jianxiang Liu2, Zhifeng Zheng4 and Can Liu1,2,3

Abstract
Boron-modified high-ortho phenolic resins (BPRs) were prepared under normal pressure by using phenol and for-
maldehyde as raw materials, zinc acetate, and oxalic acid as catalysts, and boric acid as a modifier. Boron-modified phenolic
fibers (BPFs) were prepared by melt spinning and curing in a mixture of formaldehyde and hydrochloric acid, followed by a
heat treatment under high temperature. The structure, ortho–para ratio (O/P), molecular weight and distribution,
spinnability, thermal stability, fiber strength, and morphology of the resins were characterized by Fourier transform
infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), thermo-
gravimetric analysis (TGA), scanning electron microscopy (SEM), and fiber strength testing. The results showed that the
addition of boric acid reduced the ortho reaction of the synthetic resin and the O/P value of phenolic resin. When the
content of boric acid was 3 wt%, the thermal stability was the best, the O/P value was up to 3.26, and the weight average
molecular weight (Mw) was 18745 g/mol. In Compared with the unmodified resin, the mass loss was increased by 33.7%,
and finally the carbon yield was 51.2%. The tensile strength of the fibers reached 187.2 MPa and the elongation at break
was 10.5%. By introducing boron into the molecular chain, the structure of the resin was improved, and the thermal
stability and mechanical properties of the fibers were improved.

Keywords
High-ortho, boron modification, phenolic fibers, mechanical properties

Introduction
Phenolic fiber has excellent flame retardancy properties
and has been widely used in textiles and composite mate-
rials required for special working conditions such as fire-
proof and corrosion resistance.1–4 Some other properties
of the phenolic fiber are its high carbon yield, large spe-
cific surface area, and its fiber-shape retention after car-
bonization. It can be used as the precursor of carbon fiber
and activated carbon fiber to prepare carbon fiber/pheno-
lic resin composites and energy storage materials, which
can be used in batteries, supercapacitors, microelectronic
devices and other technical fields.5–13 Phenolic fiber can
be made from thermoplastic phenolic resin through melt
spinning. Phenolic resin is a three-dimensional (3-D)
crosslinked thermosetting fiber formed after curing in a
crosslinking bath.14 Phenolic resin is brittle and has poor
spinnability due to the aromatic ring in its structure. Com-
pared with phenolic resins, high-ortho phenolic resins
have more intramolecular hydrogen bonds, which help
1
Yunnan Key Laboratory of Wood Adhesives and Glued Products,
Southwest Forestry University, Kunming, Yunnan, People’s Republic of
China
2
Key Laboratory of State Forestry Administration for Highly-Efficient
Utilization of Forestry Biomass Resources in Southwest China,
Southwest Forestry University, Kunming, Yunnan, People’s Republic of
China
3
College of Materials Science and Engineering, Southwest Forestry
University, Kunming, Yunnan, People’s Republic of China
4
College of Energy, Xiamen University, Xiamen, People’s Republic of
China
Corresponding author:
Can Liu, Yunnan Key Laboratory of Wood Adhesives and Glued Products,
Southwest Forestry University, 300 Bailong Road, Kunming, Yunnan
650224, People’s Republic of China; Key Laboratory of State Forestry
Administration for Highly-Efficient Utilization of Forestry Biomass
Resources in Southwest China, Southwest Forestry University,
Kunming, Yunnan 650224, People’s Republic of China; College of
Materials Science and Engineering, Southwest Forestry University,
Kunming, Yunnan 650224, People’s Republic of China.
Email: liucanswfu@163.com
2 High Performance Polymers XX(X)
to generate intermolecular free volume, facilitate segment
configuration movement, and better spinnability. At the
same time, the special link structure of the high-ortho-
position phenolic resin causes the retainment of the phe-
nolic hydroxyl group, thus increasing the number of
reactive sites to be more than the phenolic resins during
the curing reaction. The curing rate of the resin is higher
than that of phenolic resins because the low activation
energy and low reaction temperature of the high-ortho
resin are retained.15–22 A high-ortho position can be quan-
titatively characterized by the bonding ratio of the ortho
and para positions (O/P) of the phenolic resin. The higher
the O/P of the resin, the more the occupied ortho posi-
tions, and thus gives more structural and processing
advantages. Li et al.22 prepared two types of novolacs:
high-ortho novolacs (HOPF) with high ortho–para ratio,
and ordinary novolacs (NPF). They investigated the cure
behavior of the HOPF and HMTA with hexamethylenete-
tramine (HMTA) using DSC and TGA. The DSC analysis
confirmed that HOPF/HMTA exhibited higher reactivity
than NPF/HMTA. Li et al. 15 used sodium carbonate
(Na 2CO3) as a catalyst to prepare high-ortho phenol-
formaldehyde (HOPF) resin. With the addition of
Na2CO3, the ortho/para ratio of methylol groups increased
from 7.26 to 27.80. The prepared phenolic resin had a fast
curing rate, low curing temperature, high thermal stabi-
lity, and favorable mechanical performance. Yi et al.18
studied the effects of four metal-mediated catalysts (bar-
ium hydroxide, sodium carbonate, lithium hydroxide, and
zinc acetate) on the curing rate and temperature of phe-
nolic resin. He found out that sodium carbonate and zinc
acetate increased the reaction activity of the phenol ortho
position and the condensation reaction of ortho methylol.
During synthesis, zinc acetate could form chelating com-
pounds (containing a metal-ligand bond), which can pro-
mote the linkage of formaldehyde to the phenolic
hydroxyl ortho position.
At the same time, phenolic fiber and its derivative mate-
rials are mostly used in high-temperature environments,
which have higher requirements on the thermal and
mechanical properties of the fiber. However, the steric
effect in the curing process of phenolic fiber will cause the
oxidative cracking of the ortho-methylene group, which
worsens the heat resistance. Also, the benzene ring in the
chain segment is directly connected by the methylene,
which worsens the mechanical properties of the fiber.23
To address the above problems, boron can be introduced
into the main chain to modify the high-ortho phenolic resin
and improve the thermal stability, mechanical properties,
and electrical properties of the resin, and reduce the reac-
tivity.24–28 Boron-modified phenolic resins have been
widely studied and reported.29–37 Sun and Sun38 investi-
gated the optimization of the critical process parameters
for the preparation of boron-containing phenolic resin (B
containing PR). The highest char yield of B-containing PR
was as high as 71% under optimal conditions (molar ratios
of formaldehyde/phenol and potassium borate/phenol were
1.8 and 0.2, respectively, and reaction time was 13 h). It
was found that the boron-containing resin solution has good
wettability with carbon fiber at a concentration of 0.8 g/mL
at 35 C. Li et al.39 prepared silicon and boron-modified
phenolic resin by a simple two-step method. The maximum
decomposition rate (Dmax) decreased by about 2%/min and
the residual weight at 900 C (R900) increased by 16.7%
after the introduction of boron and silicon. The structure
of the oxidized resin was characterized to study the
mechanism of the improved thermal stability and flame
retardancy. Feng et al.40 introduced phenylboronic acid
(PBA) and two other boron compounds (4-hydroxymethyl
phenylboronic acid & boronic acid) to fabricate boron-
containing thermoplastic phenolic resins (BPRs). All the
fabricated BPRs showed higher softening points, more
excellent thermal decomposition temperature, and higher
char yield. The optimal thermal decomposition temperature
was 317.4 C and the char yield ratio at 800 C was 69.6%.
Although boron modification can improve the heat resis-
tance of the resin, its melt processability was affected,
which made it difficult to prepare the boron-modified phe-
nolic resin fibers (BPFs) and also reduced the curing speed
of the original filaments. In this study, Zn2þ was used as a
phenolic polymerization catalyst. Different boron-modified
high-ortho phenolic resins were synthesized by changing
the amount of boron. Phenolic fibers were synthesized
through the melt spinning of the synthesized resins. In this
study, nuclear magnetic resonance (NMR), gel permeation
chromatography (GPC), Fourier transform infrared (FTIR)
spectroscopy, thermogravimetry (TG), rheometry, and
scanning electron microscopy (SEM) were used to analyze
the effects of boron addition on the properties and para-
meters of the phenolic resin and phenolic resin fiber, which
provides a theoretical basis for the preparation of high-
performance phenolic fibers.
Materials and methods
Materials
Phenol, zinc acetate, oxalic acid, and boric acid were all
AR reagents purchased from Tianjin Fengchuan Chemical
Reagent Technology Co., Ltd., China. Aqueous formalde-
hyde, with a content of 37%–40%, purchased from
Chengdu Jinshan Chemical Reagent Co., Ltd., China.
Hydrochloric acid, with a content of 36%–38%, was pur-
chased from Shandian Pharmaceutical Co., Ltd., China.
Preparation process
Preparation of BPRs. The BPRs were prepared by reacting
phenol (1.0 mol) with formaldehyde (0.8 mol) in the pres-
ence of zinc acetate catalyst. First, a certain amount of
Ren et al.
phenol, formaldehyde, and zinc acetate were mixed in a
250 ml three-necked flask, which was equipped with a
reflux condenser, a stirrer, and a thermometer. The mixture
was heated and maintained at 75 C for 3 hours. Next, 2.5 g
of oxalic acid was further added and the resulting mixture
was heated to the reflux temperature for 1 hour, followed
by the addition of 1%–5% boron acid (the mass ratio of
phenol) and stirring for 2 hours. After the reaction, the
mixture was dissolved in alcohol and distilled under
vacuum to remove water and unreacted phenol at 120 C
for 2 hours. For comparison, high-ortho phenolic resin
(HOPRs) containing no boric was prepared.
Preparation of boron-modified phenolic resin fibers. The BPFs
were prepared by a melt spinning machine using the BPRs
granule at a spinning temperature of about 100 C–120 C.
The filaments were soaked in the curing solution, which
consists of 12 wt% hydrochloric acid and 18.5 wt% for-
maldehyde, and mixed properly. The resulting mixture was
then maintained for 0.5 hours at room temperature. The
curing solution was heated from room temperature to boil-
ing point at a certain heating rate and keep it for 0.5 hours.
Then, the cured fibers were further heat-treated at 180 C
for 1 hour to complete the crosslinking. For comparison,
HOPFs containing no boric was prepared.
Characterization
The infrared spectrum of HOPRs and BPRs was obtained
using a Thermo IS50 FT-TR type Fourier infrared spectro-
meter. The resin was ground and potassium bromide was
mixed and tableted for testing. NMR spectra of the samples
were obtained using the JEOL ECX 400 M spectrometer.
About 250 mg samples were dissolved in 5 ml deuterated
acetone for measurement. The methyl peak of deuterated
acetone was set to be 29 ppm from trimethylsilane (TMS).
The molecular weight of the samples was determined
through GPC. The measurement was performed on a PL-
GPC50. The sample was dissolved with N,N-
Dimethylformamide (DMF), and polystyrene (PS) was
used as the reference material. The rheological behavior
of the samples was measured using a Thermo Haake
MARS, with a cooling system under steady-state mode
with a starting temperature of 180 C and finishing tempera-
ture of 90 C. About 1.5 g of the powder sample was heated
to 180 C and cooled to 80 C to generate the viscosity-
temperature curves. Thermogravimetric analysis (TGA)
was performed on GER, TGA209 F3 thermogravimetric
analyzer. Samples were pyrolyzed in a nitrogen atmosphere
from room temperature to 800 C. The heating rate was set
at 10 C/min. The outside surface of the fibers was observed
by the HITACHI SU8010 scanning electron microscope
and the surface of the sample was treated with gold spray.
The tensile strength of the fiber was measured using the
BAIEN instrument YG005A single fiber tester. For each
3
HOPRs
1% BPRs
2% BPRs
Transmittance/％
3% BPRs
4% BPRs
5% BPRs
828 686
755
3278
1375
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber/cm-1
Figure 1. FTIR spectra of HOPRs and BPRs.
sample, 10 fibers were tested to obtain an average value.
The average length of the fibers was 10 cm.
Results and discussion
Characterization of boron-modified high-ortho
phenolic resins
Figure 1 shows the FTIR spectrum of HOPRs and BPRs.
As shown in Figure 1, the stretching vibration of the ben-
zene ring double bond in phenolic resin was around 1593
cm1, the asymmetric stretching vibration of ether bond
(C–O–C) was near 1100 cm1, the vibration of methylene
bond (–CH2–) was near 1457 cm1, and the vibration of
C–O (PhCH2–OH) in hydroxymethyl phenol was near
1040 cm1. The stretching vibration of O–H (PhO–H) in
the phenolic hydroxyl group occurs around 3278 cm1. In
comparison with HOPRs, the stretching vibration of O–H
(PhO–H) in the phenolic hydroxyl group shifted because
part of the hydroxyl group reacts with boron. An absorp-
tion peak of medium intensity occurs around 1375 cm1,
which is due to the stretching vibration of the B–O bond.
With the increase of the boric acid content, the absorption
peak had become stronger. The absorption peak near 686
cm1 was attributed to the characteristic absorption peak
of H3BO3 in BPRs.41 The absorption peak at 755 cm1
was attributed to the ortho-substituted benzene ring, and
the absorption peak at 828 cm1 was attributed to the
para-substituted benzene ring. The phenolic resins synthe-
sized with several boric acid additions all show a rela-
tively integrated area of the ortho-absorption peak
greater than the para-absorption peak.
To further characterize the ortho–para position perfor-
mance and specific O/P value of the phenolic resin, the
carbon-13 nuclear magnetic resonance (13C NMR) spectra
of the boron-modified phenolic resin with different contents
are shown in Figure 2 and Table 1, from which the molecular
4 High Performance Polymers XX(X)

13
Figure 2. C NMR spectra of HOPRs and BPRs.

Table 1. The chemical shift and O/P value of HOPRs and BPRs.

Sample O-O0 chemical shift Integral area Q-P0 chemical shift Integral area P-P0 chemical shift Integral area O/P value

0% 31 17.00 35.5 12.30 40 0.76 3.40

1% 31 13.25 35.5 11.58 40 0.78 2.98
2% 31 15.25 35.5 12.73 40 0.44 3.04
3% 31 14.90 35.5 11.32 40 0.47 3.26
4% 31 11.64 35.5 11.19 40 0.47 2.75
5% 31 16.57 35.5 17.30 40 0.30 2.73

structure can be determined. The chemical shift of solvent- (o-p0 ) of the two phenolic hydroxyl groups. The chemical
deuterated acetone was around 29 ppm. The methylene bond shifts were 31, 40, and 35.5 ppm, respectively. The phenolic
(–CH2–) in the phenolic resin was connected to the ortho hydroxyl carbon occurs between 154–158 ppm was.42 The
position (o-o0 ), para position (p-p0 ), and ortho–para position three linkage modes of methylene bond (–CH2–) are shown
Ren et al. 5

Figure 3. The structure diagram of the connection methods of methylene bond.

in Figure 3. The O/P of the boron-modified phenolic resin

5% BPRs
can be calculated using equation (1).43 4% BPRs
3% BPRs
2AO  O þ AO  P 2% BPRs
Ortho-Para ¼ ð1Þ 1% BPRs
2AP  P þ AO  P HOPRs

UV signal/mv
The Ao-o0 , Ao-p0 , and Ap-p0 are peak intensities, are Mw=20482
related to o-o0 , o-p0 , and p-p0 bonds respectively. Using
Mw=20034
equation (1), the O/P values of BPRs and HOPRs were
Mw=18745
determined as 2.98, 3.04, 3.26, 2.75, 2.73, and 3.40, respec- Mw=17586
tively. In both HOPRs and BPRs, the o-o0 bonds were Mw=17516
dominant, and the ratio of the p-p0 bonds appeared very Mw=16731
low. From Figure 2 and Table 1, it can be seen that the 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5

addition of boron leads to a downward trend in the O/P Retention Time/min

value of the resin. The analysis showed that after the

Figure 4. GPC chromatograms of HOPRs and BPRs.
boron and the phenolic hydroxyl group form the B–O bond,
the two hydroxyl groups linked on the B atom
Table 2. O/P value, molecular weight and spinning temperature
caused the ortho-position reaction to be of HOPRs and BPRs.
affected by a steric hindrance, which reduced the ortho- Melt viscosity at
position reaction probability of the phenolic resin, Sample O/P value Mn Mw Mw/Mn 120 C/mPas
increased the para-position reaction probability, and
0% 3.40 14610 16731 1.14 0.1  105
decreased the O/P value.44 At the same time, the two hydro-
1% 2.98 14983 17586 1.17 0.1  105
xyl groups (OH–B–OH) linked to the B atom can be dehy- 2% 3.04 15357 17516 1.14 0.8  105
drated with the phenolic hydroxyl group to form crosslinks, 3% 3.26 16410 18745 1.14 2  105
reducing the probability of the ortho reaction. With the 4% 2.75 17138 20034 1.16 5  105
addition of boron, the O/P value of the resin showed a 5% 2.73 17603 20482 1.16 10  105
unimodal trend. The highest O/P value of the phenolic resin
was 3.26 with 3% boric acid, which decreased to 2.73 when
the amount of boric acid was increased to 5%. At the same molecular weight distribution is uniform, with a small poly-
time, with the addition of boric acid, more Hþ ions were dispersity index (PDI), and the resin has good spinnabil-
released, and the pH of the system further dropped, which ity.46 As shown in Figure 4 and Table 2, as the boron
was beneficial to the formation of the para-structure under content increased, the number average and weight average
the strong acid system.45 It can be seen from Table 1 that molecular weight (Mn and Mw) increased with the addition
when the content of boric acid was above 3%, the O/P value of boric acid, and the molecular weight distribution
decreased significantly. Therefore, it can be concluded remained stable, indicating that the introduction of boron
from the MNR data that the resin prepared with a 3% boron into the molecular chain produced more link structures. It
content had the highest O/P value. also promoted the increase of the molecular weight, which
The molecular weight of the phenolic resin is the core was beneficial to the improvement of the mechanical and
factor in fiber preparation, and its high molecular weight thermal stability of the phenolic resin. The analysis showed
has better mechanical properties and thermal stability. The that the addition of boron led to the limitation of the ortho
6 High Performance Polymers XX(X)

reaction. The probability of the para reaction increased, and
the para reaction activity was higher, which objectively
increased the progress of the polycondensation reaction and
increased the molecular weight. However, more para reactions
would reduce the order of the resin. The molecular weight
distribution of the phenolic resin of all samples was relatively
narrow, and the addition of boric acid did not destroy the
uniformity of the molecular chain, and the narrow molecular
weight distribution was beneficial to the preparation of fibers.
To study the processability of the resin, a rheometry test
of the resin was carried out, and the results are shown in
Figure 5. As the temperature increased, the viscosity of the
resin dropped sharply. All curves had obvious turning
trends. After 140 C, the viscosity of all resins became
extremely low with no spinnability. As the boron content
increased, the molecular weight of the resin and the visc-
osity increased at the same temperature. The viscosity of
different resins at 120 C was shown in Table 2. The anal-
ysis showed that higher molecular weight leads to higher
levels of entanglement and stronger interaction between the
molecular chains. As the content of boron increased, B–O
bonds would be formed on phenolic hydroxyl groups, and
3.0x106
2.5x106
3%
2%
Viscosity/ mPa·s
further link more phenolic hydroxyl groups and molecular
chains. The formation of macromolecular chains restricted
the movement and diffusion of molecular chains. This
helped to form a larger structural network in a wider range,
which further limited the movement of cooperative segments
and increased the melt viscosity.46 Higher melt viscosity is
not conducive to the resin flow and requires higher fiber-
forming conditions. Thus the molecular weight of the resin
should not be too high, that is, the boron content should not
be too high. When the boron content was 3%, the O/P value
was the highest and similar to that of HOPRs. This indicates
that a 3% content of BPFs had more ortho structures, the
highest molecular chain linearity, and strong chain segment
moveability. The melt formed by heating had more excellent
fluidity and fiber-forming properties, suitable spinning tem-
perature, and excellent spinnability better than other BPFs.
Preparation and characterization of the phenolic fiber
The TG thermograph and its derivative (DTG) form are
shown in Figures 6 and 7, respectively. Figure 6, it can
be seen that the addition of boric acid increased the carbon
yield of the fiber precursor. The carbon yield of the resin
with the addition of 3% boric acid was the highest, 51.2%,
5%
and the resin without boric acid gave the lowest carbon
4% yield of 17.5%. It can also be seen from Figure 6 that the
pyrolysis curve of the fiber precursor had more weightless
steps. The weight loss in the range of 110 C–300 C was

2.0x106
1%
considered to be due to the weak chemical bonds in the
1.5x106 0%
boron phenolic and the decomposition of low-molecular-
1.0x106
weight resins. The DTG curve of BPFs all had a weight loss
different from that of the HOPFs around 180 C. The anal-
5.0x105 ysis showed that the boric acid did not completely react
during synthesis, and the free boron in the sample reacted
0.0
60 80 100 120 140 160 further with the phenolic hydroxyl group at high tempera-
Temperature/℃ ture to generate small molecules and water escape, which
caused a continual weight loss of the fiber. The resin with
Figure 5. The viscosity-temperature curves of HOPRs and BPRs. no boric acid addition lost less weight in this range because

Untreated fibers
100 3% BPFs
5% BPFs 0.0
2% BPFs
1% BPFs
80
4% BPFs
-0.2 Untreated fibers
HOPFs
Mass/%

1% BPFs
Mass/%

60
2% BPFs
51.2% -0.4 3% BPFs
4% BPFs
46.1%
5% BPFs
42.1%
40 -0.6 HOPFs
35.2%

23.1%
20 -0.8
17.5%
200 400 600 800 100 200 300 400 500 600 700 800
Temperature/°C Temperature/°C

Figure 6. TG curves and derivative weight of HOPFs and BPFs.

Ren et al.
100
Cured fibers
90
80
Mass/%
70
60
50
44.2%
40
100 200 300 400 500 600
Temperature/°C
Figure 7. TG curves and derivative weight of cured HOPFs and BPFs.
the resin structure was more ordered, the synthetic resin
was more uniform, and the low-molecular-weight resin and
system unreacted compounds were less. From the DTG
curves shown in Figure 6, 1% BPFs at around 180 C has
more weight loss different from other samples, which could
be attributed to the destruction of the basic resin reaction
system and the lack of a 3-D system structure dominated by
boric acid, resulting in more remnant small molecules and
degradation in this temperature range. The main weight
loss of the fiber occurred in the temperature range of
300–800 C, which was mainly due to the crosslinking reac-
tion between B–OH and PhCH2–OH, Ph–OH, etc. and
more high-bonding energy B–O bonds were introduced
into the molecular network. At the same time, a large num-
ber of tri-substituted benzene rings formed a network. In
comparison with the HOPFs resin, more degradable sub-
stances were observed at 550 C, which confirmed that the
addition of boric acid in the NMR data increased the prob-
ability of a para reaction, which increased the content of
physical conformation and thermal properties of the fiber.
On the other hand, the benzyl borate linkage replaced the
unstable phenolic hydroxyl group, which also increased the
thermal stability and delayed the thermal degradation tem-
perature of BPFs. The initial temperature of the main
weight-loss stage of HOPFs was higher than that of BPFs,
which could be because the unmodified high-ortho pheno-
lic resin had higher linearity, was completely reacted, and
did not contain unreacted residual boron. However, it can
be seen from the DTG curves in Figure 6 that the weight-
loss rate of HOPFs in the main weight-loss stage was sig-
nificantly higher than that of BPFs, and the carbon yield
was also lower than that of BPFs.
It can be seen from Figure 7 that the carbon yield of the
fiber after curing was improved, and the carbon yield of the
resin with the addition of 5% boric acid was the highest.
The HOPFs-cured fiber has the lowest carbon yield of
39.9%. Figure 7 shows the DTG curve of the cured BPFs.
7
0.0
5% BPFs
3% BPFs
2% BPFs
1% BPFs Cured fibers
Mass/%
4% BPFs
5% BPFs
HOPFs -0.2
3% BPFs
2% BPFs
4% BPFs
1% BPFs
53.8% HOPFs
-0.4
50.3%
47.5%
41.9%
39.9%
700 800 200 400 600 800
Temperature/°C
It can be seen that the curing reaction and high-temperature
heat treatment largely eliminated the pyrolysis peak of fiber
precursors below 250 C, and only a significant decomposi-
tion stage at 280–400 C, indicating that the curing reaction
and high-temperature heat treatment improved the thermal
stability of the fiber. The analysis showed that the curing
liquid (CH2O–HCl) provided excessive formaldehyde,
which enables a continual condensation reaction of the
thermoplastic resin with formaldehyde. This leads to the
formation of a 3-D crosslinked network structure that
evolves into a thermosetting resin and improves the struc-
tural stability of the fiber. At the same time, after modifica-
tion with boron, the B–O bonds were connected to the
branch of the phenolic molecule, which had a greater steric
hindrance effect and hinders the crosslinking reaction
between the CþH2OH and the phenolic molecules, made
the boric acid and CþH2OH residue. The high-temperature
heat treatment during the curing process further facilitated
the reaction between the boric acid and CþH2OH remain-
ing in the fiber. Through this reaction, a large number of
crosslinked structures were continually formed, which
enabled the completion of the crosslinking reaction and
enhanced the thermal stability of the fiber. Although the
carbon yield before and after curing was not significantly
improved, the fiber retained its shape at high temperature
after curing, which greatly increases the temperature range
that the fiber can be used. Finally, after boron modification,
the carbon yield of 5% BPFs increased by 13.9% compared
with HOPFs, and the carbon yield reached 53.8%.
Figure 8 shows the effect of the cured fiber with differ-
ent boric acid content on the tensile strength and elongation
of the fiber. After curing and heat treatment, the tensile
strength and the elongation at fiber break were both
improved with increasing boric acid content. The maxi-
mum values of the tensile strength and the elongation at
break, 187.2 MPa and 10.5%, respectively were recorded
when the boric acid content was 3%. The analysis showed
8 High Performance Polymers XX(X)
200
180
Tensile strength/Mpa
160
140
120
100
80
0 1 2 3
Figure 8. Tensile strength and elongation of cured BPFs.
3% BPFs
cured 3% BPFs
Transmittance/%
3278
4000 3500 3000
Wavenumber/cm-1
Figure 9. FTIR spectra of 3% BPFs and its cured fibers.
that as the content of boric acid increased, a large number
of borate bonds were formed when the fiber was cured. The
bond energy and bond length of the borate bonds were both
greater than the R–CH2–R methylene bridge. After the
bridge was broken, the B–O bonds were still connected,
thus this improved the mechanical strength and flexibility.
Boric acid competes for reaction sites in the reaction pro-
cess, hinders the curing reaction of CþH2OH and phenol
ring, increases the content of B–O bonds, reduces the tra-
ditional physical conformation bonding, and effectively
improves the toughness and strength of the fiber. The
mechanical properties of the fiber decrease as the content
of boric acid increases. The excess boric acid in the resin
reacts with the phenolic hydroxyl groups, which reduce the
bonding of the curing reaction, affects the resin physical
confirmation process, and reduces the spinnability,
strength, and toughness of the fiber. The comprehensive
analysis showed that the mechanical properties were the
best when the boric acid content was 3%.
Figure 9 shows the FTIR spectrum of 3% BPFs before
and after curing. It can be seen that the absorption peaks of
the main functional group of BPFs before and after curing
30 are the same. In comparison with the fiber before curing,
Strength
25
the absorption peak of the residual boric acid of the fiber at
686 cm1 after curing reaction was reduced. This indicates
20 that a small amount of boric acid participates in the reaction
Elongation/%
at high temperature during the curing process, forming a
15
stable B–O bond and a branched crosslinked thermoset
10
resin. Cured BPFs still maintained a high-ortho absorption
peak at 754 cm1. The cured fiber still retained the char-
Elongation
5 acteristics of the high-ortho-position with an undamaged
structure. All resin and fiber samples showed high-ortho
0
4 5 6 absorption peaks, indicating that the prepared phenolic
w(Boron)/%
resin materials had stable characteristic bonds before and
after curing, which made the material structure stable.
Figure 10 shows the SEM micrographs of 3% BPFs and
its cured fibers. The surface of the fiber precursor was
smooth and uniform without grooves and wrinkles, indi-
cating that there was no volatilization of ethanol and free
phenol during the formation of fiber by melt spinning.
Also, no damage was noticed for the fibers. The cross-
686
section of the precursor is uniform without holes, which
conforms to the morphology of brittle fracture. A small
amount of residue in the cross-section of the fiber precur-
sor, which may be caused by the structural adhesion of
828 uncured resin, was observed. The fiber surface of the
cured yarn was smooth without shrinkage and wrinkles.
1375 755 The fiber cross-section was found rough and concave,
showing a certain degree of toughness fracture. Because
2500 2000 1500 1000 500
of the good integrity of the cured resin, the cross-section
was clean and free of impurities. The diameter of the
uncured fiber was found to be 133.2 mm, while that of the
fiber after curing with hydrochloric acid formaldehyde
solution was 196.6 mm, which indicates fiber thickening
after curring. The analysis showed that due to the addi-
tional supplement of formaldehyde monomer in the curing
reaction, the resin further reacted and formed crosslinks
between linear molecules, which evolved into an insolu-
ble resin. In the process of the reaction, the chemical
reagents dissolved in the fiber. The water generated by
the reaction volatilized, forming a hole of about 1.6 mm,
which increased the thickness of the fiber diameter.47 The
cross-section of the cured fiber did not form a skin-core
structure, indicating that C þH2OH diffused uniformly
from the surface to the inside. With an increase in tem-
perature, the movement ability of CþH2OH increased, and
the curing process gradually became gentle. This did not
cause the slow movement of CþH2OH on the surface to
form a skin-core structure, neither did it prevent the inter-
nal solidification of the fiber. Thus, the curing bath treat-
ment and high-temperature treatment enhanced the
uniform solidification of the fiber precursor that increased
the crosslinking degree. Also, the fiber toughness and
mechanical properties of the fiber were greatly improved.
With such improvement, the brittle fracture of the primary
fiber was changed into a ductile fracture.
Ren et al.
Figure 10. SEM micrographs of 3% BPFs and its cured fibers.
Conclusion
The unique phenolic resin fiber was prepared by adding
boron element in the synthesis of phenolic resin. The con-
clusion was as follows. Phenol, formaldehyde, and boric
acid under the dual catalysis of zinc acetate and oxalic acid.
When the mass fraction of boric acid was 3%, a high-ortho
boron modification with a maximum O/P value of 3.26, a
molecular weight of 18745 g/mol, and a molecular weight
distribution of 1.14 was synthesized. The addition of boric
acid brought about the steric hindrance effect on the ortho
reaction, which reduced the probability of the ortho reac-
tion of the phenolic resin, increased the probability of the
para reaction, and decreased the O/P value of the phenolic
resin. A high-ortho boron phenolic fiber was prepared by
hydrochloric acid formaldehyde solution. The addition of
boric acid formed a B–O bond with higher bond energy and
replaced part of the unstable groups at the same time, which
improved thermal stability and mechanical properties. The
tensile strength of 3% BPFs fiber reached 187.2 MPa, and
the elongation at break was 10.5%.
Declaration of conflicting interests
The author(s) declared no potential conflicts of interest with
respect to the research, authorship, and/or publication of this
article.
Funding
The author(s) disclosed receipt of the following financial support
for the research, authorship, and/or publication of this article: This
9
work was partially supported by Supported by the National Key
Research and Development Program of China (No. 2017YF-
D0601003) and the Applied Basic Research Programs of Science
and Technology Department of Yunnan Province (Award
No.2018ZG004, 2017FG001-072, 2017FG001-001). The study
also was supported by the Key Laboratory of State Forestry
Administration for Highly-Efficient Utilization of Forestry Bio-
mass Resources in Southwest China (Southwest Forestry Univer-
sity) (No. 2019-KF05).
ORCID iDs
Yu Ren https://orcid.org/0000-0003-3678-8023
Can Liu https://orcid.org/0000-0001-9471-8002
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