Improving The Thermal and Mechanical Properties of Phenolic Fiber Over Boron Modified High-Ortho Phenolic Resin
Improving The Thermal and Mechanical Properties of Phenolic Fiber Over Boron Modified High-Ortho Phenolic Resin
Improving The Thermal and Mechanical Properties of Phenolic Fiber Over Boron Modified High-Ortho Phenolic Resin
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
1
Phenolic fiber has excellent flame retardancy properties Yunnan Key Laboratory of Wood Adhesives and Glued Products,
and has been widely used in textiles and composite mate- Southwest Forestry University, Kunming, Yunnan, People’s Republic of
China
rials required for special working conditions such as fire- 2
Key Laboratory of State Forestry Administration for Highly-Efficient
proof and corrosion resistance.1–4 Some other properties Utilization of Forestry Biomass Resources in Southwest China,
of the phenolic fiber are its high carbon yield, large spe- Southwest Forestry University, Kunming, Yunnan, People’s Republic of
cific surface area, and its fiber-shape retention after car- China
3
College of Materials Science and Engineering, Southwest Forestry
bonization. It can be used as the precursor of carbon fiber
University, Kunming, Yunnan, People’s Republic of China
and activated carbon fiber to prepare carbon fiber/pheno- 4
College of Energy, Xiamen University, Xiamen, People’s Republic of
lic resin composites and energy storage materials, which China
can be used in batteries, supercapacitors, microelectronic
Corresponding author:
devices and other technical fields.5–13 Phenolic fiber can
Can Liu, Yunnan Key Laboratory of Wood Adhesives and Glued Products,
be made from thermoplastic phenolic resin through melt Southwest Forestry University, 300 Bailong Road, Kunming, Yunnan
spinning. Phenolic resin is a three-dimensional (3-D) 650224, People’s Republic of China; Key Laboratory of State Forestry
crosslinked thermosetting fiber formed after curing in a Administration for Highly-Efficient Utilization of Forestry Biomass
crosslinking bath.14 Phenolic resin is brittle and has poor Resources in Southwest China, Southwest Forestry University,
Kunming, Yunnan 650224, People’s Republic of China; College of
spinnability due to the aromatic ring in its structure. Com- Materials Science and Engineering, Southwest Forestry University,
pared with phenolic resins, high-ortho phenolic resins Kunming, Yunnan 650224, People’s Republic of China.
have more intramolecular hydrogen bonds, which help Email: [email protected]
2 High Performance Polymers XX(X)
to generate intermolecular free volume, facilitate segment was as high as 71% under optimal conditions (molar ratios
configuration movement, and better spinnability. At the of formaldehyde/phenol and potassium borate/phenol were
same time, the special link structure of the high-ortho- 1.8 and 0.2, respectively, and reaction time was 13 h). It
position phenolic resin causes the retainment of the phe- was found that the boron-containing resin solution has good
nolic hydroxyl group, thus increasing the number of wettability with carbon fiber at a concentration of 0.8 g/mL
reactive sites to be more than the phenolic resins during at 35 C. Li et al.39 prepared silicon and boron-modified
the curing reaction. The curing rate of the resin is higher phenolic resin by a simple two-step method. The maximum
than that of phenolic resins because the low activation decomposition rate (Dmax) decreased by about 2%/min and
energy and low reaction temperature of the high-ortho the residual weight at 900 C (R900) increased by 16.7%
resin are retained.15–22 A high-ortho position can be quan- after the introduction of boron and silicon. The structure
titatively characterized by the bonding ratio of the ortho of the oxidized resin was characterized to study the
and para positions (O/P) of the phenolic resin. The higher mechanism of the improved thermal stability and flame
the O/P of the resin, the more the occupied ortho posi- retardancy. Feng et al.40 introduced phenylboronic acid
tions, and thus gives more structural and processing (PBA) and two other boron compounds (4-hydroxymethyl
advantages. Li et al.22 prepared two types of novolacs: phenylboronic acid & boronic acid) to fabricate boron-
high-ortho novolacs (HOPF) with high ortho–para ratio, containing thermoplastic phenolic resins (BPRs). All the
and ordinary novolacs (NPF). They investigated the cure fabricated BPRs showed higher softening points, more
behavior of the HOPF and HMTA with hexamethylenete- excellent thermal decomposition temperature, and higher
tramine (HMTA) using DSC and TGA. The DSC analysis char yield. The optimal thermal decomposition temperature
confirmed that HOPF/HMTA exhibited higher reactivity was 317.4 C and the char yield ratio at 800 C was 69.6%.
than NPF/HMTA. Li et al. 15 used sodium carbonate Although boron modification can improve the heat resis-
(Na 2CO3) as a catalyst to prepare high-ortho phenol- tance of the resin, its melt processability was affected,
formaldehyde (HOPF) resin. With the addition of which made it difficult to prepare the boron-modified phe-
Na2CO3, the ortho/para ratio of methylol groups increased nolic resin fibers (BPFs) and also reduced the curing speed
from 7.26 to 27.80. The prepared phenolic resin had a fast of the original filaments. In this study, Zn2þ was used as a
curing rate, low curing temperature, high thermal stabi- phenolic polymerization catalyst. Different boron-modified
lity, and favorable mechanical performance. Yi et al.18 high-ortho phenolic resins were synthesized by changing
studied the effects of four metal-mediated catalysts (bar- the amount of boron. Phenolic fibers were synthesized
ium hydroxide, sodium carbonate, lithium hydroxide, and through the melt spinning of the synthesized resins. In this
zinc acetate) on the curing rate and temperature of phe- study, nuclear magnetic resonance (NMR), gel permeation
nolic resin. He found out that sodium carbonate and zinc chromatography (GPC), Fourier transform infrared (FTIR)
acetate increased the reaction activity of the phenol ortho spectroscopy, thermogravimetry (TG), rheometry, and
position and the condensation reaction of ortho methylol. scanning electron microscopy (SEM) were used to analyze
During synthesis, zinc acetate could form chelating com- the effects of boron addition on the properties and para-
pounds (containing a metal-ligand bond), which can pro- meters of the phenolic resin and phenolic resin fiber, which
mote the linkage of formaldehyde to the phenolic provides a theoretical basis for the preparation of high-
hydroxyl ortho position. performance phenolic fibers.
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 Materials and methods
mechanical properties of the fiber. However, the steric
effect in the curing process of phenolic fiber will cause the Materials
oxidative cracking of the ortho-methylene group, which Phenol, zinc acetate, oxalic acid, and boric acid were all
worsens the heat resistance. Also, the benzene ring in the AR reagents purchased from Tianjin Fengchuan Chemical
chain segment is directly connected by the methylene, Reagent Technology Co., Ltd., China. Aqueous formalde-
which worsens the mechanical properties of the fiber.23 hyde, with a content of 37%–40%, purchased from
To address the above problems, boron can be introduced Chengdu Jinshan Chemical Reagent Co., Ltd., China.
into the main chain to modify the high-ortho phenolic resin Hydrochloric acid, with a content of 36%–38%, was pur-
and improve the thermal stability, mechanical properties, chased from Shandian Pharmaceutical Co., Ltd., China.
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- Preparation process
gated the optimization of the critical process parameters Preparation of BPRs. The BPRs were prepared by reacting
for the preparation of boron-containing phenolic resin (B phenol (1.0 mol) with formaldehyde (0.8 mol) in the pres-
containing PR). The highest char yield of B-containing PR ence of zinc acetate catalyst. First, a certain amount of
Ren et al. 3
Transmittance/%
of oxalic acid was further added and the resulting mixture
3% BPRs
was heated to the reflux temperature for 1 hour, followed
by the addition of 1%–5% boron acid (the mass ratio of 4% BPRs
phenol) and stirring for 2 hours. After the reaction, the
mixture was dissolved in alcohol and distilled under 5% BPRs
828 686
vacuum to remove water and unreacted phenol at 120 C
for 2 hours. For comparison, high-ortho phenolic resin 755
3278
1375
(HOPRs) containing no boric was prepared.
4000 3500 3000 2500 2000 1500 1000 500
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
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
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
reaction. The probability of the para reaction increased, and further link more phenolic hydroxyl groups and molecular
the para reaction activity was higher, which objectively chains. The formation of macromolecular chains restricted
increased the progress of the polycondensation reaction and the movement and diffusion of molecular chains. This
increased the molecular weight. However, more para reactions helped to form a larger structural network in a wider range,
would reduce the order of the resin. The molecular weight which further limited the movement of cooperative segments
distribution of the phenolic resin of all samples was relatively and increased the melt viscosity.46 Higher melt viscosity is
narrow, and the addition of boric acid did not destroy the not conducive to the resin flow and requires higher fiber-
uniformity of the molecular chain, and the narrow molecular forming conditions. Thus the molecular weight of the resin
weight distribution was beneficial to the preparation of fibers. should not be too high, that is, the boron content should not
To study the processability of the resin, a rheometry test be too high. When the boron content was 3%, the O/P value
of the resin was carried out, and the results are shown in was the highest and similar to that of HOPRs. This indicates
Figure 5. As the temperature increased, the viscosity of the that a 3% content of BPFs had more ortho structures, the
resin dropped sharply. All curves had obvious turning highest molecular chain linearity, and strong chain segment
trends. After 140 C, the viscosity of all resins became moveability. The melt formed by heating had more excellent
extremely low with no spinnability. As the boron content fluidity and fiber-forming properties, suitable spinning tem-
increased, the molecular weight of the resin and the visc- perature, and excellent spinnability better than other BPFs.
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 Preparation and characterization of the phenolic fiber
levels of entanglement and stronger interaction between the The TG thermograph and its derivative (DTG) form are
molecular chains. As the content of boron increased, B–O shown in Figures 6 and 7, respectively. Figure 6, it can
bonds would be formed on phenolic hydroxyl groups, and be seen that the addition of boric acid increased the carbon
yield of the fiber precursor. The carbon yield of the resin
3.0x106
with the addition of 3% boric acid was the highest, 51.2%,
5%
and the resin without boric acid gave the lowest carbon
2.5x106 4% yield of 17.5%. It can also be seen from Figure 6 that the
3% pyrolysis curve of the fiber precursor had more weightless
2%
steps. The weight loss in the range of 110 C–300 C was
Viscosity/ mPa·s
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
100
Cured fibers 0.0
5% BPFs
90 3% BPFs
2% BPFs
1% BPFs Cured fibers
80
Mass/%
4% BPFs
5% BPFs
Mass/%
HOPFs -0.2
3% BPFs
70
2% BPFs
4% BPFs
60 1% BPFs
53.8% HOPFs
-0.4
50 50.3%
47.5%
44.2%
41.9%
40
39.9%
100 200 300 400 500 600 700 800 200 400 600 800
Temperature/°C Temperature/°C
the resin structure was more ordered, the synthetic resin It can be seen that the curing reaction and high-temperature
was more uniform, and the low-molecular-weight resin and heat treatment largely eliminated the pyrolysis peak of fiber
system unreacted compounds were less. From the DTG precursors below 250 C, and only a significant decomposi-
curves shown in Figure 6, 1% BPFs at around 180 C has tion stage at 280–400 C, indicating that the curing reaction
more weight loss different from other samples, which could and high-temperature heat treatment improved the thermal
be attributed to the destruction of the basic resin reaction stability of the fiber. The analysis showed that the curing
system and the lack of a 3-D system structure dominated by liquid (CH2O–HCl) provided excessive formaldehyde,
boric acid, resulting in more remnant small molecules and which enables a continual condensation reaction of the
degradation in this temperature range. The main weight thermoplastic resin with formaldehyde. This leads to the
loss of the fiber occurred in the temperature range of formation of a 3-D crosslinked network structure that
300–800 C, which was mainly due to the crosslinking reac- evolves into a thermosetting resin and improves the struc-
tion between B–OH and PhCH2–OH, Ph–OH, etc. and tural stability of the fiber. At the same time, after modifica-
more high-bonding energy B–O bonds were introduced tion with boron, the B–O bonds were connected to the
into the molecular network. At the same time, a large num- branch of the phenolic molecule, which had a greater steric
ber of tri-substituted benzene rings formed a network. In hindrance effect and hinders the crosslinking reaction
comparison with the HOPFs resin, more degradable sub- between the CþH2OH and the phenolic molecules, made
stances were observed at 550 C, which confirmed that the the boric acid and CþH2OH residue. The high-temperature
addition of boric acid in the NMR data increased the prob- heat treatment during the curing process further facilitated
ability of a para reaction, which increased the content of the reaction between the boric acid and CþH2OH remain-
physical conformation and thermal properties of the fiber. ing in the fiber. Through this reaction, a large number of
On the other hand, the benzyl borate linkage replaced the crosslinked structures were continually formed, which
unstable phenolic hydroxyl group, which also increased the enabled the completion of the crosslinking reaction and
thermal stability and delayed the thermal degradation tem- enhanced the thermal stability of the fiber. Although the
perature of BPFs. The initial temperature of the main carbon yield before and after curing was not significantly
weight-loss stage of HOPFs was higher than that of BPFs, improved, the fiber retained its shape at high temperature
which could be because the unmodified high-ortho pheno- after curing, which greatly increases the temperature range
lic resin had higher linearity, was completely reacted, and that the fiber can be used. Finally, after boron modification,
did not contain unreacted residual boron. However, it can the carbon yield of 5% BPFs increased by 13.9% compared
be seen from the DTG curves in Figure 6 that the weight- with HOPFs, and the carbon yield reached 53.8%.
loss rate of HOPFs in the main weight-loss stage was sig- Figure 8 shows the effect of the cured fiber with differ-
nificantly higher than that of BPFs, and the carbon yield ent boric acid content on the tensile strength and elongation
was also lower than that of BPFs. of the fiber. After curing and heat treatment, the tensile
It can be seen from Figure 7 that the carbon yield of the strength and the elongation at fiber break were both
fiber after curing was improved, and the carbon yield of the improved with increasing boric acid content. The maxi-
resin with the addition of 5% boric acid was the highest. mum values of the tensile strength and the elongation at
The HOPFs-cured fiber has the lowest carbon yield of break, 187.2 MPa and 10.5%, respectively were recorded
39.9%. Figure 7 shows the DTG curve of the cured BPFs. when the boric acid content was 3%. The analysis showed
8 High Performance Polymers XX(X)
200 30 are the same. In comparison with the fiber before curing,
180
Strength
25
the absorption peak of the residual boric acid of the fiber at
686 cm1 after curing reaction was reduced. This indicates
Tensile strength/Mpa
Elongation/%
at high temperature during the curing process, forming a
140 15
stable B–O bond and a branched crosslinked thermoset
120 10
resin. Cured BPFs still maintained a high-ortho absorption
peak at 754 cm1. The cured fiber still retained the char-
Elongation
100 5 acteristics of the high-ortho-position with an undamaged
structure. All resin and fiber samples showed high-ortho
80 0
0 1 2 3 4 5 6 absorption peaks, indicating that the prepared phenolic
w(Boron)/%
resin materials had stable characteristic bonds before and
Figure 8. Tensile strength and elongation of cured BPFs.
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
3% BPFs smooth and uniform without grooves and wrinkles, indi-
cured 3% BPFs
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-
Transmittance/%
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,
3278
showing a certain degree of toughness fracture. Because
4000 3500 3000 2500 2000 1500 1000 500
of the good integrity of the cured resin, the cross-section
Wavenumber/cm-1
was clean and free of impurities. The diameter of the
Figure 9. FTIR spectra of 3% BPFs and its cured fibers. 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
that as the content of boric acid increased, a large number after curring. The analysis showed that due to the addi-
of borate bonds were formed when the fiber was cured. The tional supplement of formaldehyde monomer in the curing
bond energy and bond length of the borate bonds were both reaction, the resin further reacted and formed crosslinks
greater than the R–CH2–R methylene bridge. After the between linear molecules, which evolved into an insolu-
bridge was broken, the B–O bonds were still connected, ble resin. In the process of the reaction, the chemical
thus this improved the mechanical strength and flexibility. reagents dissolved in the fiber. The water generated by
Boric acid competes for reaction sites in the reaction pro- the reaction volatilized, forming a hole of about 1.6 mm,
cess, hinders the curing reaction of CþH2OH and phenol which increased the thickness of the fiber diameter.47 The
ring, increases the content of B–O bonds, reduces the tra- cross-section of the cured fiber did not form a skin-core
ditional physical conformation bonding, and effectively structure, indicating that C þH2OH diffused uniformly
improves the toughness and strength of the fiber. The from the surface to the inside. With an increase in tem-
mechanical properties of the fiber decrease as the content perature, the movement ability of CþH2OH increased, and
of boric acid increases. The excess boric acid in the resin the curing process gradually became gentle. This did not
reacts with the phenolic hydroxyl groups, which reduce the cause the slow movement of CþH2OH on the surface to
bonding of the curing reaction, affects the resin physical form a skin-core structure, neither did it prevent the inter-
confirmation process, and reduces the spinnability, nal solidification of the fiber. Thus, the curing bath treat-
strength, and toughness of the fiber. The comprehensive ment and high-temperature treatment enhanced the
analysis showed that the mechanical properties were the uniform solidification of the fiber precursor that increased
best when the boric acid content was 3%. the crosslinking degree. Also, the fiber toughness and
Figure 9 shows the FTIR spectrum of 3% BPFs before mechanical properties of the fiber were greatly improved.
and after curing. It can be seen that the absorption peaks of With such improvement, the brittle fracture of the primary
the main functional group of BPFs before and after curing fiber was changed into a ductile fracture.
Ren et al. 9
5. Duan L, Zhao X and Wang Y. Oxidation and ablation beha- 20. Shudo Y, Izumi A, Takeuchi T, et al. Dynamic light scatter-
viors of carbon fiber/phenolic resin composites modified with ing study of the curing mechanisms of novolac-type phenolic
borosilicate glass and polycarbosilane interface. J Alloys resins. Polym J 2015; 47: 428–433.
Compd 2020; 827: 154277. 21. Xu Y, Guo L, Zhang H, et al. Research status, industrial
6. Ahmadijokani F, Shojaei A, Arjmand M, et al. Effect of short application demand and prospects of phenolic resin. RSC Adv
carbon fiber on thermal, mechanical and tribological behavior 2019; 9: 28924–28935.
of phenolic-based brake friction materials. Compos B Eng 22. Li C, Bu Z, Sun J, et al. New insights into high-ortho phenolic
2019; 168: 98–105. novolac: elucidating dependence between molecular struc-
7. Feng A, Jia Z, Yu Q, et al. Preparation and characterization of ture, curing kinetics and thermal stability. Thermochim Acta
carbon nanotubes/carbon fiber/phenolic composites on 2013; 557: 77–86.
mechanical and thermal conductivity properties. Nano 23. Bian C, Wang S, Liu Y, et al. Thermal stability of phenolic
2018; 13: 1850037. resin: new insights based on bond dissociation energy and reac-
8. Xie G, Chen Z, Ramakrishna S, et al. Orthogonal design tivity of functional groups. RSC Adv 2016; 6: 55007–55016.
preparation of phenolic fiber by melt electrospinning. J Appl 24. Wang S, Wang Y, Bian C, et al. The thermal stability and
Polym Sci 2015; 132: 42574. pyrolysis mechanism of boron-containing phenolic resins: the
9. Choi GG, Oh SJ, Lee SJ, et al. Production of bio-based phe- effect of phenyl borates on the char formation. Appl Surf Sci
nolic resin and activated carbon from bio-oil and biochar 2015; 331: 519–529.
derived from fast pyrolysis of palm kernel shells. Bioresour 25. Kai Y, Mingli J, Xiaomei Z, et al. Structure, stability, and
Technol 2015; 178: 99–107. properties of phenolic fibers modified by phenyl molybdate.
10. Krüner B, Schreiber A, Tolosa A, et al. Nitrogen-containing Polym Polym Compos 2020. DOI: 10.1177/09673911
novolac-derived carbon beads as electrode material for super-
20927801.
capacitors. Carbon 2018; 132: 220–231.
26. Wang F, Huang Z, Liu Y, et al. Novel cardanol-containing
11. Ebrahimi H, Roghani-Mamaqani H and Salami-Kalajahi M.
boron-modified phenolic resin composites: non-isothermal
Preparation of carbon nanotube-containing hybrid compo-
curing kinetics, thermal properties, and ablation mechanism.
sites from epoxy, novolac, and epoxidized novolac resins
High Perform Polym 2017; 29: 279–288.
using sol–gel method. J Therm Anal Calorim 2018; 132:
27. Ding J, Huang Z, Qin Y, et al. The effect of boron in-
513–524.
corporation on the thermo-oxidative stability of phenol-
12. Joon S, Kumar R, Singh AP, et al. Lightweight and solution
formaldehyde resin and its pyrolyzate phase. In: 2015 Inter-
processible thin sheets of poly (o-toluidine)-carbon fiber-
national Conference on Materials, Environmental and Bio-
novolac composite for EMI shielding. RSC Adv 2015; 5:
logical Engineering, Guilin, China, 28 March–30 March
55059–55065.
2015. Atlantis Press. DOI:10.2991/mebe-15.2015.234.
13. Romanoski GR, Lach K, Monaghan K, et al. An investigation
28. Bian C, Wang Y, Wang S, et al. Influence of borate structure
of the rheological behavior of phenolic resins considered for
on the thermal stability of boron-containing phenolic resins: a
production of carbon bonded carbon fiber insulation. In:
Nuclear and Emerging Technologies for Space, American DFT study. Polym Degrad Stabil 2015; 119: 190–197.
Nuclear Society Topical Meeting, Richland, Washington, 25 29. Zhang L, Zhang Y, Wang L, et al. Phenolic resin modified by
February–28 February 2019. http://anstd.ans.org. boron-silicon with high char yield. Polym Test 2019; 73:
14. Economy J and Clark RA.Fibers from novolacs. Patent 208–213.
3650102, USA, 1972. 30. Feng J, Li J, Chen L, et al. Enhanced thermal stabilities and
15. Li J, Zhu W, Zhang J, et al. Curing properties of high-Ortho char yields of carbon fibers reinforced boron containing
phenol-formaldehyde resins with co-catalysis. J Appl Polym novolac phenolic resins composites. J Polym Res 2017;
Sci 2019; 136: 47229. 24: 176.
16. Asim M, Saba N, Jawaid M, et al. A review on phenolic resin 31. Yun J, Chen L, Zhang X, et al. The effect of introducing B
and its composites. Curr Anal Chem 2018; 14: 185–197. and N on pyrolysis process of high ortho novolac resin. Poly-
17. Emik S, Yılmaz BY and Iyim_ TB. Investigation of the usage mers 2016; 8: 35.
of depolymerized nylon 66 intermediate in phenolic resin 32. Jiao ML, Yang K, Cao J, et al. Effect of boron content of
modification. Polym Plast Technol Mater 2019; 58: high-ortho phenolic fibers on thermal property. Therm Sci
454–463. 2015; 19: 1411–1414.
18. Yi Z, Zhang J, Zhang S, et al. Synthesis and mechanism of 33. Li C, Ma Z, Zhang X, et al. Silicone-modified phenolic resin:
metal-mediated polymerization of phenolic resins. Polymers relationships between molecular structure and curing beha-
2016; 8: 159. vior. Thermochim Acta 2016; 639: 53–65.
19. Hu XM, Zhao YY and Cheng WM. Effect of formaldehyde/ 34. Weißhuhn J, Seifert A, Dzhagan V, et al. B2O3/SiO2/phenolic
phenol ratio (F/P) on the properties of phenolic resins and resin hybrid materials produced by simultaneous twin poly-
foams synthesized at room temperature. Polym Compos merization of spiromonomers. Macromol Chem Phys 2018;
2015; 36: 1531–1540. 219: 1700487.
Ren et al. 11
35. Wang F, Huang Z and Guo Z. Bionic boron/silicon-modified 41. Chen B, Yu J, Zhou Y, et al. Preparation, structure and prop-
phenolic resin system with multifunctional groups: synthesis, erties of boron modified high-ortho phenolic fibers. Fibers
thermal properties and ablation mechanism. Biosurf Biotribol Polym 2016; 17: 678–686.
2018; 4: 85–93. 42. Nomoto M, Fujikawa Y, Komoto T, et al. Structure and cur-
36. Yi X, Feng A, Shao W, et al. Synthesis of boron modified ing mechanism of high-ortho and random novolac resins as
phenolic resin and the mechanic performance of its molding studied by NMR. J Mol Struct 2010; 976: 419–426.
plastics. Mater Rev 2015; 16: 52–57. 43. Zhou D, Liu D, Wang H, et al. Nonisothermal curing beha-
37. Ganesh Babu T and Devasia R. Boron-modified phenol viors of novolac-type phenolic resins of varied ortho to para
formaldehyde resin-based self-healing matrix for ratios. Polym Plast Technol Eng 2011; 50: 983–989.
C f /SiBOC composites. Adv Appl Ceram 2016; 115: 44. Kawamoto AM, Pardini LC, Diniz MF, et al. Synthesis of a
457–469. boron modified phenolic resin. J Aerosp Technol Manag
38. Sun Y and Sun Y. Strong effect of process parameters on the 2010; 2: 169–182.
properties of boron-containing phenolic resins with high char 45. Huang J, Xu M, Ge Q, et al. Controlled synthesis of high-
yield. Appl Sci 2020; 10: 1408. ortho-substitution phenol–formaldehyde resins. J Appl Polym
39. Li S, Chen F, Zhang B, et al. Structure and improved thermal Sci 2005; 97: 652–658.
stability of phenolic resin containing silicon and boron ele- 46. Ying YG, Pan YP, Ren R, et al. Effect of the molecular struc-
ments. Polym Degrad Stabil 2016; 133: 321–329. ture of phenolic novolac precursor resins on the properties of
40. Feng J, Chen L, Gu J, et al. Synthesis and characterization of phenolic fibers. Mater Chem Phys 2013; 143: 455–460.
aryl boron-containing thermoplastic phenolic resin with high 47. Liu CL, Ying YG, Feng HL, et al. Microwave promoted rapid
thermal decomposition temperature and char yield. J Polym curing reaction of phenolic fibers. Polym Degrad Stabil 2008;
Res 2016; 23: 97. 93: 507–512.