molecules
Article
Preparation of Lignin-Based High-Ortho Thermoplastic
Phenolic Resins and Fibers
Yu Ren 1 , Jin Xie 1 , Xiahong He 2 , Rui Shi 2, * and Can Liu 1,2, *






Citation: Ren, Y.; Xie, J.; He, X.; Shi,
R.; Liu, C. Preparation of
Lignin-Based High-Ortho
Thermoplastic Phenolic Resins and
Fibers. Molecules 2021, 26, 3993.
https://doi.org/10.3390/
molecules26133993
Academic Editors: Xiaohui Wang and
Chuanfu Liu
Received: 18 May 2021
Accepted: 26 June 2021
Published: 30 June 2021
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4.0/).
Molecules 2021, 26, 3993. https://doi.org/10.3390/molecules26133993
1 Key Laboratory for Forest Resources Conservation and Utilization in the Southwest Mountains of China,
College of Materials Science and Engineering, Southwest Forestry University, Kunming 650224, China;
ry159@outlook.com (Y.R.); Xj920721256@163.com (J.X.)
2 Key Laboratory of State Forestry Administration for Highly-Efficient Utilization of Forestry Biomass
Resources in Southwest China, Southwest Forestry University, Kunming 650224, China;
hexiahong@hotmail.com
* Correspondence: shirui@swfu.edu.cn (R.S.); liucan@swfu.edu.cn (C.L.)
Abstract: Surplus lignin, which is inefficiently used, is generated in the forestry industry. Currently,
most studies use lignin instead of phenol to synthesize thermosetting resins which cannot be repro-
cessed, thus affecting its application field. Thermoplastic phenolic resin has an orderly structure
and excellent molding performance, which can greatly improve its application field and economic
value. Herein, phenol was partially replaced with enzymolysis lignin (without treatment), generating
lignin-based high-ortho thermoplastic phenolic resins (LPRs), and then lignin-based phenolic fibers
(LPFs) were prepared by melt spinning. FTIR, 13 C-NMR and GPC were used to characterize the
ortho–para position ratio (O/P value), molecular weight and its distribution (PDI), and rheological
properties of the resin. TG, XRD, SEM and tensile property studies were used to determine the
thermal stability, orientation, and surface morphology of the fiber. Lignin addition resulted in the
decline of the O/P value and molecular weight of the resin. For the 10% LPR, the O/P value, Mw,
and PDI were 1.28, 4263, and 2.74, respectively, with the fiber exhibiting relatively good spinnability.
The tensile strength and elongation at break of the 10% LPF were 160.9 MPa and 1.9%, respectively.
The addition of lignin effectively improved the thermal properties of the fiber, and the carbon yields
of 20% LPF before and after curing were 39.7% and 53.6%, respectively, which were 22.2% and 13.7%
higher than that of the unmodified fiber, respectively.
Keywords: lignin; thermoplastic phenolic resin; high-ortho; phenolic fiber; thermal stability
1. Introduction
In the context of global energy depletion and environmental pollution, research and
development regarding biomass energy and materials is particularly critical. In the field
of lignocellulosic biomass, cellulose and hemicellulose have been widely studied and
applied in the preparations of bioethanol, furan compounds, and carbon-based materials
through various biological and chemical pathways [1–3]. However, lignin, as the second
largest bio-based polymer material and the largest source of natural aromatics, has not
been well-utilized and is generally produced as a low-value by-product of cheap energy [4].
Lignin has a phenylpropane structure similar to that of phenol; therefore, it has strong
potential to replace phenol in phenolic resin synthesis [5,6]. Pinheiro [7] used the acetic acid
solvent method to extract lignin instead of phenol from bagasse at 187 ◦ C and used 95%
acetic acid to prepare phenolic resin. Compared with sulfate lignin, these lignins exhibited
higher thermal stability, lower molar mass, and lower methoxyl content, and were therefore
suitable for phenolic resin synthesis. Wang [8] used a novel solid acid catalytic crystal-
lization process to treat enzymatic hydrolysis lignin (EHL), which reduced the molecular
weight of the EHL and improved the phenolic hydroxyl content and reaction activity. The
treated lignin replaced 50% of the phenol, generating phenolic foam that showed good
https://www.mdpi.com/journal/molecules
Molecules 2021, 26, 3993 2 of 12

heat insulation and compressive strength. Li [9] conducted low-cost depolymerization of

alkaline lignin and elucidated the polymerization mechanism. Compared with basic lignin
phenolic resin, the phenolic resin prepared using depolymerized lignin cured faster, with
good bonding strength. However, there are currently two problems with the application of
lignin in phenolic resins: For improvement, lignin has to be further depolymerized, and
the procedures are cumbersome and costly. Conversely; the previous research regarding
lignin phenolic resin mostly focuses on phenolic foam, adhesives, and other thermosetting
resins. The poor processability of the resin limits its applicability [10–12].
Thermoplastic phenolic resin displays excellent processability, may considerably
improve the applicability and thus the value of the resin, and may be synthesized under
acidic conditions. Chemical thermoplastic phenolic resins are widely used in phenolic
molding powder, foam plastic, and fiber. Of these, phenolic fiber is a type of 3D cross-linked
heat-resistant fiber, which is prepared from thermoplastic phenolic resin by melt spinning
and solidifying in a coagulation bath. It was discovered during research into cheap carbon
fiber necessary for aerospace applications [13]. Phenolic fiber displays a relatively high
limiting oxygen index (34–36%) and excellent flame retardant performance, maintaining the
original molecular chain structure after high-temperature combustion. Fabric consisting of
phenolic fiber has unique advantages in high-temperature protection, aerospace equipment
protection, and other fields [14–20]. Meanwhile, phenolic fiber is also a precursor in the
preparation of activated carbon fiber and carbon fiber/phenolic resin composites, which
have been widely used in adsorption and energy storage materials, and in electrochemical
fields [20,21]. The wide application of these fibers requires specific parameters of the
phenolic resin, such as a narrow molecular weight distribution index and high proportion
of linear arrangement. During thermoplastic phenolic resin synthesis, methylene may react
at the ortho or para positions on the phenol ring. When more ortho connections occur
than para connections (i.e., the O/P value is higher than 1), a high-ortho phenolic resin is
formed [22,23]. The high-ortho phenolic resin structure is more ordered, while the highly
reactive para-position group is retained, which results in faster curing [24–29]. Therefore,
the special structure of high-ortho resin is more conducive to phenolic fiber preparation.
In general, the preparation of lignin polymer materials may expand the applicability
and considerably improve the economic value of lignin, and numerous studies regarding
thermoplastic lignin polymers have been reported [30–36]. Chen [37] added freeze-dried
alkali lignin to polypropylene by melt compounding. The increased interfacial areas
and superior dispersity values significantly improved the mechanical properties of the
composites, and lignin promoted the ultraviolet and oxidation resistances of the composites.
Wang [38] prepared lignin/polylactic acid (PLA) fibers by melt spinning, showing that the
introduction of PLA improved the composite spinnability, and the hydrogen bonds formed
between the materials improved the tensile modulus of the carbon fiber. Kai [39] prepared
lignin-poly (3-hydroxybutyrate) (PHB) composite nanofibers by grafting β-butyrolactone
onto lignin. The addition of lignin improved the tensile strength, elongation, and Young’s
modulus of the fiber, which exhibited good antioxidant properties and biocompatibility.
In the above studies, lignin and thermoplastic polyolefins were blended to prepare lignin
thermoplastics. Lignin molecules do not generally react in resin compositions; at the same
time, there has been little research regarding lignin thermoplastic phenolic resins. Our team
prepared thermoplastic phenolic resin from early-stage lignin liquefaction and discussed
its application in fibers [40,41]. In previous studies, lignin liquefaction products were used
in resin syntheses. However, high temperatures and strong acids were required for lignin
liquefaction, and the preparation steps were complicated, the process was dangerous, and
there were various complex problems, such as acid treatment. The process was neither
simple nor green. To utilize lignin more efficiently, it is necessary to further simplify the
resin synthesis and improve its machinability.
In this study, thermoplastic lignin-based phenolic resin was synthesized by partially
replacing phenol with enzymatic hydrolysis lignin, and the phenolic fiber was prepared
by melt spinning. The effects of different lignin contents on the resin structure and fiber
 the process was dangerous, and there were various complex problems, such as acid treat-
ment. The process was neither simple nor green. To utilize lignin more efficiently, it is
necessary to further simplify the resin synthesis and improve its machinability.
Molecules 2021, 26, 3993 In this study, thermoplastic lignin-based phenolic resin was synthesized by partially
3 of 12
replacing phenol with enzymatic hydrolysis lignin, and the phenolic fiber was prepared
by melt spinning. The effects of different lignin contents on the resin structure and fiber
properties were investigated by adding lignin directly without treatment. The results lay
properties were investigated by adding lignin directly without treatment. The results lay a
a theoretical foundation for the synthesis of high-performance lignin thermoplastic phe-
theoretical foundation for the synthesis of high-performance lignin thermoplastic phenolic
nolic resin and efficient lignin utilization.
resin and efficient lignin utilization.
2. Results
2. Results and
and Discussion
Discussion
2.1. Characterization of LPRs
2.1. Characterization of LPRs
2.1.1. FT-IR
2.1.1. FT-IR Characterization
Characterization of
of the
the LPRs
LPRs
Figure
Figure11 shows
shows thethe FT-IR
FT-IRspectra
spectraof of the
the LPRs
LPRs containing
containingdifferent
differentlignin
lignincontents.
contents.The
The
O–H (PhO-H) of the phenolic hydroxyl group is observed at ~3325 cm −1−1. The stretching
O–H (PhO-H) of the phenolic hydroxyl group is observed at ~3325 cm . The stretching
vibration −−1
1 , and the absorption
vibrationof ofthe
thebenzene
benzenering ringdouble
doublebondsbondsisisobserved
observedatat~1593 ~1593cm cm , and the absorption
peak − 1
peak of the benzene
benzene ring ringsubstituent
substituentisisobserved
observedatat~1511 ~1511 cmcm. With
−1 . With increasing
increasing lignin
lignin con-
content,
tent, the the absorption
absorption peak peak intensity
intensity increases,
increases, because
because a larger
a larger amount amount of lignin
of lignin reacts
reacts with
with the benzene
the benzene ring toring
formtosubstituent
form substituent
groups.groups. The deformation
The deformation vibration vibration of the
of the methylene
methylene bond (–CH –) is observed at ~1455 cm −1 , the asymmetric stretching vibration of
bond (–CH2–) is observed 2 at ~1455 cm , the asymmetric stretching vibration of the ether
−1

the
bondether bond (C–O–C)
(C–O–C) is observed is observed
at ~1100atcm ~1100 cm−the
−1, and
1 , and the vibration of C–O(PhCh –OH)
vibration of C–O(PhCh2–OH) 2in hy-
in hydroxymethyl phenol is observed −1 . The absorption peak observed−1
droxymethyl phenol is observed at ~1040atcm ~1040
−1. The cm absorption peak observed at ~827 cm
at − 1
~827 cm therepresents the para-substituted 756 cm−1 , the ortho-
represents para-substituted benzene ring, benzene and at 756 ring,
cm−1and, theatortho-substituted ben-
substituted benzene ring.
zene ring. Compared with Compared
the IR spectra with of the IR spectra
high-ortho of high-ortho
phenolic resin (HOPR), phenolic
the resin
char-
(HOPR),
acteristicthe characteristic
absorption peaksabsorption
of LPR arepeaks
almost ofidentical,
LPR are almost identical,
indicating that theindicating that the
overall phenolic
overall phenolic resin structure is largely unaffected by the addition
resin structure is largely unaffected by the addition of lignin. However, with increasing of lignin. However,
with increasing lignin content, the ortho-absorption −1
lignin content, the ortho-absorption peak observed peak at 756observed at 756 cm
cm−1 decreases, whiledecreases,
the para-
while the para-absorption − 1
absorption peak observedpeak observed
at 827 at 827 cm showing
cm−1 increases, increases, showing
a decline in aortho-substituted
decline in ortho-
substituted
products. The products.
methoxy The methoxy
group group
of lignin of lignin
occupies theoccupies the ortho
ortho position position
relative relative
to the to
phenolic
the phenolic
hydroxyl hydroxyl
group, and thus group, and
exerts thus exerts
a steric effect ona steric effectreaction
the ortho on the ortho
of the reaction of the
resin, inducing
resin, inducing the decrease in the fraction
the decrease in the fraction of the ortho product. of the ortho product.

20% LPR

15% LPR
Transmittance (%)

10% LPR

5% LPR

HOPR

827
1511 756

4000 3500 3000 2500 2000 1500 1000

Wavenumber (cm-1)

Figure 1.
Figure 1. FT-IR
FT-IR spectra
spectra of
of LPRs
LPRs with
withdifferent
differentlignin
ligninsubstitution
substitutionrates.
rates.

2.1.2. 13 C-NMR Analysis of the LPRs

2.1.2. 13C-NMR Analysis of the LPRs
To
To further characterizethe
further characterize theortho/para
ortho/para structures
structures and
and obtain
obtain more
moreaccurate
accurateO/P
O/P val-
val-
ues for the lignin phenolic resins, the 13 C-NMR spectra of the phenolic resins containing
ues for the lignin phenolic resins, the C-NMR spectra of the phenolic resins containing
13
different
differentlignin
lignincontents
contentsare
areshown
shown inin
Figure 2. The
Figure chemical
2. The shift
chemical of the
shift solvent,
of the deuterated
solvent, deuter-
acetone, is observed at approximately 29 ppm. The signals representing the methylene
bonds (–CH2 –), corresponding to ortho–ortho (O–O’), para–para (P–P’), or ortho–para
(O–P’) connections within the phenolic resin, are observed at 31, 40, and 35.5 ppm, respec-
tively. The signals at 155–150 ppm are assigned to C1 connected to the phenolic hydroxyl
group, while those observed at 134–126.5 ppm represent ortho- and para-C linked with
CH2 and the meta position C3 not involved in the reaction. The signals observed at 119–121
and ~115 ppm represent unreacted para-C4 and unreacted ortho-C2, respectively. The
 AO–O’, AO–P’, and AP–P’ are the intensities of the signals representing the O–O’,
O–P’, and P–P’ bonds, respectively. The calculated O/P values of the LPRs and HOPR are
1.55, 1.28, 1.26, 1.15, and 3.40. After lignin addition, the O/P ratio of the resin decreases
significantly, and with increasing lignin content, the O/P ratio decreases gradually. When
Molecules 2021, 26, 3993 4 of 12
the lignin content is 20%, the resin almost no longer displays the characteristics of high-
ortho-substitution, which is consistent with FT-IR spectroscopy. The 13C-NMR spectra of
HOPR and 20% LPR (Figure 2b) suggest that the carbon skeletons of the resins are almost
identical aftermodes
three linking the addition of lignin.(–CH
of methylene However, there are two weak signals observed at ~65
2 –) are shown in Figure 1. The O/P values of the
and ~91 ppm for 20% LPR that are not observed
resins are calculated using the following Equation in(1)
the[42].
spectrum of HOPR, and the struc-
ture represented by these two signals exhibits a similar linkage to that of carbon atoms
within lignin [43]. Hence, lignin is involved
O/P value =
2AOin −
phenolic − P synthesis, generating com-
O + AOresin
(1)
plex molecular chains, and does not form a2AP − P physical
simple + AO − Pmixture.

Figure
Figure 2.
2. (a)
(a) The 13C-NMR
The 13 C-NMRspectra
spectra of
of LPRs
LPRs with
with different
different lignin
lignin replacement
replacement amounts (5–20%); (b)
amounts (5–20%); (b) difference
difference of
of 13
13C-NMR
C-NMR
spectra of lignin before and after the resin reaction (20% LPR and HOPR).
spectra of lignin before and after the resin reaction (20% LPR and HOPR).

2.1.3.AO–O’,
Molecular Weights
AO–P’, and(GPC)
AP–P’and are Spinnabilities
the intensitiesofofthe
theLPRs
signals representing the O–O’,
O–P’,Figure
and P–P’ bonds, respectively. The calculated O/P
3a shows the gel chromatograms of the LPRs containing values of the LPRs andlignin
different HOPRcon-are
1.55, 1.28, 1.26, 1.15, and 3.40. After lignin addition, the O/P ratio
tents. The number average molecular weight, weight average molecular weight, molecu- of the resin decreases
significantly,
lar and with increasing
weight distribution (PDI) and lignin content,
O/P values the resins
of the O/P ratio decreases
are shown gradually.
in Table 1. TheWhen
mo-
the lignin content is 20%, the resin almost no longer displays the characteristics
lecular weight of phenolic resin affects the fiber-forming property and, subsequently, the of high-
ortho-substitution,
fiber properties. Thewhich
largeristheconsistent
molecular with FT-IR
weight ofspectroscopy. The 13 C-NMR
the resin, the stronger spectra
the thermal andof
HOPR and 20% LPR (Figure 2b) suggest that the carbon skeletons of the
mechanical properties of the resin, and the narrower the PDI, which is conducive to fiber resins are almost
identical after
preparation. the addition
Compared withof lignin.
that However,
of HOPR, there are
the relative two weak
molecular signals
weights observed
of the LPRs are at
~65 and ~91 ppm for 20% LPR that are not observed in the spectrum
not large, and the average molecular weights of the LPRs decrease with increasing lignin of HOPR, and the
structureThis
content. represented
may be by these two
because the signals exhibitsofa similar
large amount methoxyl linkage
withinto that
ligninof causes
carbon anatoms
in-
within in
crease lignin [43]. Hence,oflignin
the proportion is involved in phenolic
the monofunctional system resin
within synthesis, generating
the reaction, whichcomplex
inhibits
molecular chains, and
polycondensation. Thisdoes not formmolecular
terminates a simple physical
chain growthmixture.and decreases the formation
2.1.3. Molecular Weights (GPC) and Spinnabilities of the LPRs
Figure 3a shows the gel chromatograms of the LPRs containing different lignin con-
tents. The number average molecular weight, weight average molecular weight, molecular
weight distribution (PDI) and O/P values of the resins are shown in Table 1. The molecular
weight of phenolic resin affects the fiber-forming property and, subsequently, the fiber
properties. The larger the molecular weight of the resin, the stronger the thermal and
mechanical properties of the resin, and the narrower the PDI, which is conducive to fiber
preparation. Compared with that of HOPR, the relative molecular weights of the LPRs
are not large, and the average molecular weights of the LPRs decrease with increasing
lignin content. This may be because the large amount of methoxyl within lignin causes an
increase in the proportion of the monofunctional system within the reaction, which inhibits
polycondensation. This terminates molecular chain growth and decreases the formation
of the macromolecular chains, thus decreasing the molecular weights of the LPRs. Simul-
taneously, the system contains more free phenols, and therefore easily generates small
molecules, resulting in the reduction in the weight-average molecular weight. This results
in an incomplete phenolic reaction and thus facilitates the generation of small molecules
within the system, thus broadening the PDI and resulting in a decrease in spinnability.
Upon phenolic resin synthesis, the links are not simple and linear, the original linear struc-
ture is destroyed, and the spinnability deteriorates, because the lignin does not undergo

Molecules 2021, 26, 3993
molecules, resulting in the reduction in the weight-average molecular weight. This result
in an incomplete phenolic reaction and thus facilitates the generation of small molecule
within the system, thus broadening the PDI and resulting in a decrease in spinnability
Upon phenolic resin synthesis, the links are not simple and linear, the original5 linear of 12 struc
ture is destroyed, and the spinnability deteriorates, because the lignin does not underg
liquefaction, depolymerization, and other treatments, but maintains the original, mor
complex, networkdepolymerization,
liquefaction, structure. Among andthe LPRs,
other 10% LPR
treatments, exhibits the
but maintains narrowest
the original, morePDI, wit
complex, network structure. Among the LPRs, 10% LPR exhibits the narrowest PDI,
a high molecular weight and O/P value and good spinnability relative to those of the othe with
a high molecular weight and O/P value and good spinnability relative to those of the
LPRs. other LPRs.

(b)
(a) 4.0x105
10
20% LPR 3.5x105
Mw:3853 15% LPR
20% LPR
8
10% LPR 3.0x105 15% LPR
10% LPR

Viscosity (mPas)
Mw:4059 5% LPR
6 2.5x105 5% LPR
UV signal (mv)

HOPR
Mw:4263 HOPR
4 Mw:4528 2.0x105
Mw:14,929
1.5x105
2
1.0x105
0
5.0x104
-2 solvent
0.0
0 2 4 6 8 10 12 14
80 100 120 140 160
Retention time (min)
Temperature (℃)

Figure 3. (a) GPC chromatograms of LPRs and HOPR; (b) the viscosity-temperature curves of LPRs and HOPR.
Figure 3. (a) GPC chromatograms of LPRs and HOPR; (b) the viscosity-temperature curves of LPRs and HOPR.
Table 1. O/P value, PDI and molecular weight of LPRs and HOPR.
Table 1. O/P value, PDI and molecular weight of LPRs and HOPR.
Sample O/P Value Mn Mw PDI

Sample0% 3.40
O/P Value 12,736
Mn PDI 14,929Mw 1.17
5% 1.55 1350 4528 3.36
0% 10% 3.40
1.28 12,736
1553 1.17 14,929
4263 2.74
5% 15% 1.26
1.55 1324
1350 3.36 40594528 3.06
20% 1.15 1373 3853 2.80
10% 1.28 1553 4263 2.74
15%To study the processing
1.26 properties of1324 4059 the spinning tem-
the resins and determine 3.06
20%
peratures of the LPRs,1.15
rheological studies 1373 3853
were performed (Figure 2.80
3b). With increasing
temperature, the viscosities of the resins decreased sharply, and the curves all exhibited a
transformation. Above 140 ◦ C, the viscosities of all resins were very low, the resins
Toclear
study the processing properties of the resins and determine the spinning tempe
became fluids, and no longer exhibited spinnability. Prior to fluidization, at the same
atures temperature,
of the LPRs,therheological studies
higher the lignin weretheperformed
content, (Figureof3b).
higher the viscosity theWith increasing
resin, which is tem
perature, the viscosities
negatively correlated of thetheresins
with decreased
relative sharply,
molecular weight and
of the theThe
resin. curves all exhibited
structure of lignin a clea
transformation. Above
itself is complex, and 140
the°C, the viscosities
synthesized LPR does ofnot
allpossess
resins awere very
strong low,
linear the resins
structure such becam
as that of regular phenolic resin. When softened using heat, the motion
fluids, and no longer exhibited spinnability. Prior to fluidization, at the same temperatur of the molecular
segments containing the lignin structure is restricted, resulting in uneven heating of the
the higher the lignin content, the higher the viscosity of the resin, which is negatively co
resin due to poor fluidity, and thus showing higher viscosity at the same temperature.
relatedWhen
withthethelignin
relative molecular
content is more thanweight10%,ofhigh
theviscosity
resin. The
andstructure of lignin
poor spinnability areitself
still is com
plex, and the synthesized
observed when heated to LPR ◦
120 does not possess
C. A longer heatingatime
strong linear
or higher structure
spinning such as that o
temperature
is required to render the resin more fluid, which increases the challenge
regular phenolic resin. When softened using heat, the motion of the molecular segment of the spinning
process. Ten percent LPR exhibited a high MW, relatively narrow PDI, high O/P value,
containing the lignin structure is restricted, resulting in uneven heating of the resin du
and good spinnability at 100–110 ◦ C. Therefore, 10% LPR is the optimal raw material for
to poorthefluidity,
preparationandof thus showing
lignin-based higher
phenolic fiberviscosity
(LPF). at the same temperature. When th
lignin content is more than 10%, high viscosity and poor spinnability are still observe
2.2. Characterization
when heated to 120 °C.ofAthe LPFs heating time or higher spinning temperature is require
longer
2.2.1. TG–DTG Characterization of the LPFs
to render the resin more fluid, which increases the challenge of the spinning process. Te
Figure 4 shows the TG–DTG thermograms of the LPFs containing different lignin
percent LPR exhibited a high MW, relatively narrow PDI, high O/P value, and good spin
contents. With increasing temperature, the LPFs maintained continuous mass losses with
nability at 100–110
multiple mass °C.
loss Therefore,
steps, which10%
mainlyLPR is the optimal
manifested in threeraw material
stages. for stage,
In the first the preparatio
at
of lignin-based
~100–300 C,◦ phenolic
the massfiber
loss is(LPF).
mainly caused by the evaporation of residual water within
 contents. With increasing temperature, the LPFs maintained continuous mass losses w
multiple mass loss steps, which mainly manifested in three stages. In the first stage,
~100–300 °C, the mass loss is mainly caused by the evaporation of residual water with
Molecules 2021, 26, 3993 the resin, the further condensation reaction of the resin, and the decompositions 6 of 12 of seve
small molecules. During this stage, the mass losses of 5% LPF and high-ortho pheno
fiber (HOPF) are clearer, indicating that lignin addition reduces the mass loss here. Lign
was added
the resin,tothe
the system
further at the beginning
condensation of resin,
reaction of the the reaction and fully mixed
and the decompositions with phen
of several
replacing
small several
molecules. small
Duringmolecules
this stage,that did not
the mass undergo
losses of 5% LPF condensation
and high-ortho reactions,
phenolic and th
fiber (HOPF) are clearer, indicating that lignin addition reduces
improving the thermal stability of the resin. Higher lignin content results in the mass loss here. Lignin
a more sta
was added to the system at the beginning of the reaction and fully mixed with phenol,
thermogram of the resin. In the second stage, at ~300–450 °C, most of the resin commen
replacing several small molecules that did not undergo condensation reactions, and thus
decomposition
improving the into hydrogen,
thermal stability ofcarbon dioxide,
the resin. water,
Higher lignin and results
content other in small
a more molecules,
stable in
catedthermogram
by a largeofmass loss.In During
the resin. the second this stage,
stage, the highest
at ~300–450 ◦ C, mostmass
of theloss
resiniscommences
observed, and t
rate of mass loss of
decomposition the
into LPFs clearly
hydrogen, carbon increases, indicating
dioxide, water, and other that
smallthe thermal
molecules, stability of L
indicated
is lowest, between 300 and 450 °C. This is caused by the complex structure ofoflignin d
by a large mass loss. During this stage, the highest mass loss is observed, and the rate
mass loss of the LPFs clearly increases, indicating that the thermal stability of LPF is lowest,
rupting the linear structure of phenolic resin. However, the preparation and uses of
between 300 and 450 ◦ C. This is caused by the complex structure of lignin disrupting the
fiber linear
all occur below
structure 300 °C.resin.
of phenolic Therefore,
However,the the preparations
preparation and and properties
uses of the fiber allof the pheno
occur
fibersbelow
are largely◦ unaffected.
300 C. Therefore, In the third
the preparations andstage, at 450–800
properties °C, the
of the phenolic fiber
fibers arecommences
largely c
unaffected.
bonization, withInonly
the third
HOPF stage, at 450–800a ◦relatively
exhibiting C, the fiber clear
commences carbonization,
mass loss during this withstage. D
to theonly HOPF exhibiting a relatively clear mass loss during this stage. Due to the complex
complex molecular structure of lignin and the large carbon–carbon bond energy
molecular structure of lignin and the large carbon–carbon bond energy in part of the
part of the structure,
structure, a higher temperature
a higher temperature is required for is required forwhich
decomposition, decomposition,
eventually increaseswhich even
ally increases
the carbon theyieldcarbon
of LPF. yield of LPF.

(a) (b)
Untreated fibers
100 0.0
20% LPF
Derivative Weight (%/min)

90 15% LPF
10% LPF
80 5% LPF -0.1
70 HOPF
Mass (%)

Untreated fibers
60 -0.2 20% LPF
15% LPF
50 10% LPF
39.7% 5% LPF
40 -0.3 HOPF
38.1%
30 32.0%
30.2%
20 -0.4
17.5%
10
100 200 300 400 500 600 700 800 900 100 200 300 400 500 600 700 800
Temperature (℃) Temperature (°C)

FigureFigure
4. (a) 4.
TG (a)curves of LPFs
TG curves of LPFsand
andHOPF; (b)DTG
HOPF; (b) DTG curves
curves of LPFs
of LPFs and HOPF.
and HOPF.

The TG–DTG thermograms of the cured fibers after coagulation-bath and high-
The TG–DTG thermograms of the cured fibers after coagulation-bath and high-te
temperature treatment are shown in Figure 5. The carbon yields of the cured LPFs were
perature treatment
improved, with thearecarbon
shown in of
yield Figure
the 20% 5. LPF
Thebeingcarbonthe yields
highest.of In the cured LPFs
comparison with were i
proved, with
Figure the carbon
4, curing yield of the 20%
and high-temperature LPF being
treatment theeliminated
largely highest. In thecomparison
first-stage masswith Figu
lossesand
4, curing of the fibers and increasedtreatment
high-temperature their main largely
decomposition stage temperatures.
eliminated the first-stage The de- losses
mass
composition stages are not clear until 350 ◦ C, indicating that curing and high-temperature
the fibers and increased their main decomposition stage temperatures. The decompositi
treatment improve the thermal stabilities of the fibers. Similarly, as shown in Figure 5a,
stageslignin
are addition
not clearincreases
until 350
the °C, indicating
thermal stabilitiesthat curing
of the curedand high-temperature
fibers, and the increase in treatm
improve
ligninthe thermal
content stabilities
is positively of thewith
correlated fibers.
the Similarly, as shown
thermal stability, which in Figure 5a,
is consistent lignin ad
with
the thermal stabilities of the uncured fibers. Lignin in this study did not
tion increases the thermal stabilities of the cured fibers, and the increase in lignin cont undergo additional
treatment;correlated
is positively therefore, thewith
aromatic
the structure
thermalofstability,
lignin waswhich
largely is
retained and thewith
consistent thermal
the therm
properties in the resin system were improved. According to Figure 6c, the increase in
stabilities of the
unreactive uncured
lignin fibers.
components Lignin
within the in this
resin study
affects thedid not undergo
continuity additional
of the resin, leading totreatme
therefore, the aromatic structure of lignin was largely
a decrease in the tensile strength and elongation at break of the fiber.retained and the thermal propert
 in the resin system were improved. According to Figure 6c, the increase in unreactive lig-
Molecules 2021, 26, 3993 7 of 12
Molecules 2021, 26, x FOR PEER REVIEW 7 of 12
nin components within the resin affects the continuity of the resin, leading to a decrease
in the tensile strength and elongation at break of the fiber.
in the resin system were improved. (b)According to Figure 6c, the increase in unreactive lig-
(a) nin components within the resin affects0.1 the continuity of the resin, leading to a decrease
110
in the tensileCured
strength
fibersand elongation at break of the fiber.
100 20% LPF 0.0

Derivative Weight (%/min)

15% LPF (b)
(a) 0.1
90 110 10% LPF
-0.1
Cured fibers
5% LPF
100 20% LPF 0.0 Cured fibers

Derivative Weight (%/min)

80 HOPF
Mass (%)

15% LPF 20% LPF

90 10%-0.2
LPF 15% LPF
70 -0.1
5% LPF
80 HOPF
10%
CuredLPF
fibers
Mass (%)

20% LPF
5% LPF
60 -0.3 -0.2 15% LPF
70 HOPF
53.6% 10% LPF
51.8% 5% LPF
50 60 -0.3
53.6% HOPF
44.8% -0.4
50 51.8%
42.5%
40 44.8% -0.4
39.9% 42.5%
40
-0.5
39.9%
30 100 -0.5
200 300 400 300 500 600 700 800800
100 200 300 400 30
500 600200 700
300 800 900 600 100 200 400 500 600 700
100 400 500 700 800 900
Temperature (°C) Temperature (°C) Temperature (°C) (°C)
Temperature

Figure 5. (a) Figure

TG curves ofTG
5. (a) cured LPFsofand
curves HOPF;
cured LPFs(b)
andDTG curves
HOPF; (b) of
DTGcured LPFsofand
curves HOPF.
cured LPFs and HOPF.
Figure 5. (a) TG curves of cured LPFs and HOPF; (b) DTG curves of cured LPFs and HOPF.
(a) (b) (c)
200
(b)
Untreated 10% LPF (c)
Untreated 10% LPF 18
Cured 10% LPF 200
Cured 10% LPF 180
F
Tensile strength (MPa)
10% LPR Strength
Untreated 10% LPF 1815
Transmittance (%)

(%)
180 160
756 Cured 10% LPF
Intensity (a.u.)

Tensile strength (MPa)

Strength 12

ElongationElongation
10% LPR 15
140

(%)
160 9
756
Intensity (a.u.)

120 12
6
822 140 Elongation
100 93

120 80 0
0 5 10 15 20 6
4000 3500 3000 2500 2000 1500 1000 20 40 60 80
822 Elongation
Lignin (%)
Wavenumber (cm-1) 2θ (°) 100 3
Figure 6.
Figure 6. (a) FT-IR
FT-IR spectra
spectra of
of 10%
10% LPF
LPF before
before and
and after
after curing;
curing; (b)
(b) XRD
XRD images
images of
of 10%
10% LPR
LPR and
and 10%
10% LPF
LPF before
before and
and after
after
80 0
curing; (c)
curing; (c) tensile
tensile strength
strength and
and elongation
elongationof
of cured
curedLPFs.
LPFs. 0 5 10 15 20
0 2000 1500 1000 20 40 60 80 Lignin (%)
mber (cm-1) 2.2.2. Characterization
2.2.2. 2θ (°)
Characterization of Structural
of Structural and and Tensile
Tensile Properties
Properties of of the
the LPFs
LPFs
Figure 6a
Figure 6a shows
shows thethe IR
IR spectra
spectra of of the
the 10%
10% LPFLPF before
before and
and after
after curing.
curing. TheThe absorption
absorption
R spectra of 10% LPF before and after
peaks curing;
of the main(b) functional
XRD images groups of of
10%the LPR
fibers and
before10% and LPF
after before
curing and
are after iden-
almost
peaks of the main functional groups of the fibers before and after curing are almost identical,
strength and elongation of curedbecause
LPFs.
tical, because the curing
the curing doesinvolve
does not not involve an additional
an additional curingcuring
agentagent (e.g., methenamine),
(e.g., methenamine), with
with only formaldehyde solution providing the
only formaldehyde solution providing the free hydroxymethyl group free hydroxymethyl group to complete
to complete the
the curing,
curing, which which
does does
not not generate
generate a new a structure.
new structure.After After
curing, curing,
the the spectrum
spectrum of the of the
cured
2.2.2. Characterization of Structural and Tensile Properties of the LPFs
curedstill
fiber fiberdisplays
still displays
strongstrong absorption
absorption peakspeaks
at 756 at cm
756−1cm andand
−1
822822
cmcm −1 .−1. Through
Through the the
Figure 6a showsintegration
the IR spectra
integration of the of the
respective 10%
peaks LPF
and before
the and
calculation after
of thecuring.
relative
of the respective peaks and the calculation of the relative O/P values, the O/P The
O/P absorption
values, the O/P
value
value of
of the
the
peaks of the main functional groups fiber before
fiber before curing
curing
of the is 1.88,
is
fibers 1.88, whereas
whereas
before and theO/P
the O/P value
after value
curing of the
of thearefiber
fiber after curing
after
almost curing
iden- is
is
1.81. This is because the reactivity of the aromatic ring at the para position
1.81. This is because the reactivity of the aromatic ring at the para position of the group is of the group is
tical, because the curing
higher,
does
higher, which not
which leads involve
leads toto the an additional
the relative
relative increase
increase in curing
in the agent
the intensity
intensity of of the(e.g.,
the para methenamine),
para position
position peakpeak and
and
with only formaldehyde solution
the decrease in theproviding
O/P value
O/P value of the
of the freeafter
the fiber
fiber hydroxymethyl
after curing.
curing. group to complete
the curing, which does In notthegenerate
XRD patterns a new(Figurestructure.
6b), the resinAfter
and two curing, the spectrum
fibers exhibit fronts
the diffuse frontsof the of
of
amorphous substances, and no crystal changes occur during the preparation and curing
cured fiber still displays strong absorption peaks at 756 cm−1 and
of the fibers. The phenolic resin displays a low-order bond
822 preparation
bond structure,
cm−1with
structure, with
. Through and curing
the
the structural
the structural
integration of the respective peaks and
disorder increasing afterthe calculation
lignin of thethe
doping. Therefore, relative
preparation O/Pofvalues,
the fiberthe doesO/P
does not
not
increase the order.
order. During
During curing,
curing, body-shape
body-shape cross-linking
value of the fiber before curing is 1.88, whereas the O/P value of the fiber after curing is
cross-linking occurs,
occurs, and
and the
the orientation
orientation
prepared and and cured
1.81. This is because does not change. Therefore, the prepared
the reactivity of the aromatic ring atcured fibers are
the fibers
para are amorphous
amorphous structures.
position of thestructures.
group is
Figure 6c shows the tensile strengths and elongations at break of the fibers containing
higher, which leads to the relative
different increase
lignin contents. Afterin the and
curing intensity of the with
heat treatment, paraincreasing
position peak
lignin and
content,
the decrease in the O/P value of the fiber after curing.
In the XRD patterns (Figure 6b), the resin and two fibers exhibit the diffuse fronts of
amorphous substances, and no crystal changes occur during the preparation and curing
Molecules 2021, 26, 3993 8 of 12

Figure 6c shows the tensile strengths and elongations at break of the fibers containing
different lignin contents. After curing and heat treatment, with increasing lignin content,
the tensile strength and elongation at break of the fiber initially increased and then de-
creased. The homogeneity and continuity of the resin of the blank sample were superior
because of the absence of lignin, and the tensile strength of the fiber decreased after the
addition of lignin. When the lignin content was 10%, the tensile strength and elongation at
break reached the maxima of 160.9 MPa and 1.9%, respectively. In general, the elongation
at break did not change much. According to the Mw and PDI data of LPRs, the PDI of 10%
LPR was the smallest, while the molecular weight was relatively high. Similarly, according
to the DTG data of LPF, the peak of 10% LPF was relatively small, which also indicates
the homogeneity of the resin composition. All of these factors had a positive effect on
the tensile strength of 10% LPF. The end-capping effect of lignin resulted in the lower
molecular weight of the phenolic resin with high lignin content. The complex structure of
lignin rendered the molecular chain non-uniform, the PDI was wide, and the fluidity and
spinnability of the molecular chain deteriorated. Meanwhile, no modifier was added to the
LPF, and the molecular chain structure with higher bond energy was not generated during
curing, resulting in poor fracture strength and toughness of the fiber.

2.2.3. SEM Characterization of the LPFs

The SEM images of the surfaces and cross sections of the 10% and 20% LPFs are shown
in Figure 7. The fiber surfaces were smooth (Figure 7a–c), but there were small amounts
of residue, which may have been caused by small-molecule decompositions on the fiber
surfaces in strong acid during curing. More surface residue was observed on the cured 20%
LPF, which is due to the high lignin content and the small molecular components within the
fiber structure, which generate more residues on the fiber surface, resulting in a decrease
in the smoothness of the fiber surface. The cross section of the cured 10% LPF (Figure 7e)
displays ductile fractures with different fracture directions, indicating that curing and heat
treatment improved the degree of cross-linking within the fiber and increased the strength
and toughness of the fiber. There are a small number of residues and tiny holes in the cross
section, which were due to the volatilization of the chemical reagents dissolved in the fiber
and the water generated by the reaction during curing, in addition to the incompletely
cured resin structure when the fracture adhesion formed residue. Although the cross
section of the cured 20% LPF also exhibited some ductile fracture, it had a core–shell
structure. This is due to the lignin complex structure resulting in the slow diffusion of
C+ H2 OH ions from the fiber surface to the interior. With increasing temperature, the curing
rate was accelerated, the outer layer of the fiber gradually solidified, and the movement
of C+ H2 OH ions was hindered. The internal solidification of the fiber was incomplete,
and finally decomposed in the strong acid during curing at high temperature, forming the
core–shell structure. This is also the main reason for the lower fracture strength of the 20%
LPF relative to that of the 10% LPF. Thus, the replacement amount of lignin should not be
too high. When the replacement amount of lignin was 10%, the performance of the LPF
was optimal.
OR PEERMolecules
REVIEW 2021, 26, 3993 9 of 12 9 of 12

Figure
Figure 7. SEM
7. SEM micrographs
micrographs of the and
of the surface surface
cross and
sectioncross section
of the 10% LPFofand
the20%
10%LPF.
LPF and
(a,d) 20% and
surface LPF. (a,d)ofsur-
section 10%
face(b,e)
LPF; andsurface
section
andof 10% of
section LPF;
10%(b,e) surface
LPF cured and
fiber; (c,f)section of 10%
surface and LPF
section cured
of 20% LPFfiber;
cured(c,f)
fiber.surface and sec-
tion of 20% LPF cured fiber.
3. Materials and Methods
3. Materials and 3.1. Chemicals
Methods
All chemicals used were obtained as follows: zinc acetate, oxalic acid, sulfuric acid,
3.1. Chemicals and hydrochloric acid were purchased from Titan Technology (Shanghai, China); ethanol,
phenol,
All chemicals used and aqueous
were obtained 37–40% formaldehyde
as follows: were purchased
zinc acetate, oxalicfrom
acid,Tianjin Zhiyuan
sulfuric acid,Chemi-
cal Reagent Co. (Tianjin, China). Lignin, ground to 100–120 mesh, was purchased from
and hydrochloric acid were purchased from Titan Technology (Shanghai, China); ethanol,
Yunnan Yunjinglin Paper (Puer, China). All chemicals were of analytical grade and used
phenol, and aqueouswithout
37–40% formaldehyde
further purification. were purchased from Tianjin Zhiyuan Chem-
ical Reagent Co. (Tianjin, China). Lignin, ground to 100–120 mesh, was purchased from
3.2. Preparation
Yunnan Yunjinglin Paper (Puer, China). All chemicals were of analytical grade and used
without further purification. and lignin (5, 10, 15, or 20 g) were added to a three-point◦ flask equipped with
Phenol
a reflux condenser, thermometer, and an agitator, and heated at 120 C for 0.5 h to ensure
complete mixing. Subsequently, 4.4 g zinc acetate and 65 g formaldehyde solution were
3.2. Preparation added, and the reaction continued for 3 h. Finally, 2.5 g oxalic acid was added, and the
mixture
Phenol and lignin was
(5, 10, heated
15, or 20tog)reflux
weretemperature
added to afor 3 h. The mixture
three-point was then dissolved
flask equipped with in
organic solvent and
a reflux condenser, thermometer, anddecompressed
an agitator, toandremove water
heated and unreacted
at 120 °C for 0.5phenol. After 2 h of
h to ensure
precipitation, the LPR was obtained.
complete mixing. Subsequently, 4.4 g zinc
LPF was prepared acetatetheand
by spinning 65 g resin
modified formaldehyde solution
particles in a melt were
spinning machine
added, and the reaction continued
◦ for 3 h. Finally, 2.5 g oxalic acid was added,
at 100–120 C. Fibrous precursors were soaked in a coagulation bath consisting ofand the
12 wt.%
mixture was heatedhydrochloric
to reflux temperature
acid and 18.5 for 3 formaldehyde,
wt.% h. The mixture wasevenly,
mixed then and
dissolved in or-
maintained at room
temperature for to
ganic solvent and decompressed 0.5remove
h. The curing
watersolution was heatedphenol.
and unreacted from room temperature
After to boiling
2 h of pre-
at a heating rate of 20 ◦ C/h and maintained for 1 h. Finally, the cured fibers were further
cipitation, the LPR was obtained. ◦
heat-treated at 180 C for 1 h to complete cross-linking.
LPF was prepared by spinning the modified resin particles in a melt spinning ma-
chine at 100–120 °C.3.3. Characterization
Fibrous precursors were soaked in a coagulation bath consisting of
12 wt.% hydrochloric acid and 18.5 wt.%was
FT-IR spectroscopy performed using
formaldehyde, a Nicolet
mixed iS50 FT-IR
evenly, spectrometer (Thermo
and maintained at
Fisher Scientific, Waltham, MA, USA) with the KBr tablet method in the scan range
room temperature for 0.5 h. The curing solution was heated from room temperature to
4000–400 cm−1 with 64 scans. Then, 13 C-NMR spectroscopy was performed using an
boiling at a heating ECZ
rate 400S
of 20NMR
°C/hinstrument
and maintained for 1Japan).
(JEOL, Tokyo, h. Finally,
The 50the
mg cured
samplesfibers were in
were dissolved
further heat-treateddeuterated
at 180 °C acetone.
for 1 h The
to complete cross-linking.
methyl peak of deuterated acetone was set to 29 ppm. GPC was
conducted using a PL-GPC 50 gel chromatograph (Agilent Technologies, Santa Clara, CA,
3.3. Characterization USA) with 20 mg sample dissolved in N,N-dimethylformamide, while polystyrene was
used as the reference material. The rheological studies were performed using the Haake
FT-IR spectroscopy was performed using a Nicolet iS50 FT-IR spectrometer (Thermo
Fisher Scientific, Waltham, MA, USA) with the KBr tablet method in the scan range 4000–
400 cm−1 with 64 scans. Then, 13C-NMR spectroscopy was performed using an ECZ 400S
NMR instrument (JEOL, Tokyo, Japan). The 50 mg samples were dissolved in deuterated
Molecules 2021, 26, 3993 10 of 12

Mars iQ rotational rheometer (Thermo Fisher Scientific). A 1.5 g powder sample was heated
to 180 ◦ C and cooled to 90 ◦ C in steady-state mode to generate the viscosity–temperature
curve. TG–DTG was conducted using a TG 209 F3 Tarsus (NETZSCH, Selb, Germany).
Samples of 10 mg were heated at 10 ◦ C/min in the temperature range 50–800 ◦ C with
nitrogen as the protective gas at a flow rate of 20 mL/min. XRD was performed using
an UItima IV X–ray diffractometer (Rigaku, Tokyo, Japan) with the sample scanned in
the 2θ range 5–60◦ . An SU8010 scanning electron microscope (Hitachi, Tokyo, Japan) was
used for SEM at an accelerating voltage range of 0.02–30 kV and a working distance of
8.5 mm under vacuum, and the sample was treated with gold spray. The tensile strengths
of the fibers were measured using a Baien YG005A electronic single fiber strength machine
(Wenzhou, China). The sample was a single fiber 10 cm in length, the tensile speed was
10 mm/min, the pretension was 0.2 N, and the initial tension was 5 N. Each sample was
tested 10 times to obtain an average value.

4. Conclusions
LPRs containing different lignin contents (5%, 10%, 15%, or 20%) were prepared by
the partial substitution of phenol through direct addition, and LPFs were then successfully
prepared. Structural analyses of the prepared LPRs showed that lignin participated in the
resin reaction and did not form a simple physical mixture. Lignin addition resulted in a
decrease in the O/P value, and the complex structure and sealing effect of lignin resulted in
a decrease in the molecular weight and an increase in the PDI. For example, the molecular
weight of the 10% LPR was 4263, the PDI was 2.74, and the spinning temperature was
100–110 ◦ C with good spinnability. Lignin improved the thermal stability of the fiber, and
the carbon yields of the 20% LPF before and after curing were 39.7% and 53.6%, respectively,
which were 22.2% and 13.7% higher than those of unmodified fiber, respectively. Lignin
had a considerable influence on the fiber morphology, with residue observed on the fiber
surface and micro-holes in the cross section. When the replacement amount of lignin was
20%, a core–shell structure was observed, which reduced the fiber strength and toughness.
The fiber morphology and tensile properties of the 10% LPF were optimal, with a tensile
strength of 160.9 MPa and an elongation at break of 1.9%. In our previous work, phenolic
fibers were prepared using lignin liquefaction [41]. The O/P values of the LPRs were lower
than those of the resins prepared using liquefaction, and the average molecular weights
of the LPRs were smaller. Due to the complex structure of lignin, the resin synthesized
directly using lignin exhibited poor continuity, the core-shell structure was observed in
the cured fiber, and the tensile strength of the fiber was relatively low. Although the fiber
prepared using liquefaction was superior, the direct addition of lignin considerably reduces
the preparation complexity and costs and considerably improves the possibility of using
LPRs for industrial applications.

Author Contributions: Conceptualization, Y.R., R.S. and C.L.; methodology, Y.R. and J.X.; writing—
original draft preparation, Y.R.; writing—review and editing, R.S. and C.L.; visualization, Y.R.;
supervision, R.S.; project administration, C.L.; funding acquisition, X.H. All authors have read and
agreed to the published version of the manuscript.
Funding: This work was partially supported by the National Key Research and Development Pro-
gram of China (No. 2017YFD0601003); the Applied Basic Research Programs of Science and Technol-
ogy Department of Yunnan Province (Award No. 202101AT070041, 2019ZG00901, 202002AA10007);
Yunnan Provincial High-end Foreign Experts Program of Thousand Talents Program (2019013),
Yunnan Provincial Financial Forestry Science and Technology Promotion Demonstration Special
Project in 2020 (2020) TS09.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Molecules 2021, 26, 3993 11 of 12

Conflicts of Interest: The authors declare no conflict of interest.

Sample Availability: Samples of the compounds are available from the authors.

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