processes

Article
Improving Epoxy Resin Performance Using PPG and MDI by
One-Step Modification
Yong Wen 1,2, *, Xudong Liu 2 and Lang Liu 1

1 State Key Laboratory of Chemistry and Utilization of Carbon Based Energy Resources, College of Chemistry,
Xinjiang University, Urumqi 830017, China; liulang@xju.edu.cn
2 School of Civil Engineering and Architecture, Xinjiang University, Urumqi 830047, China;
230208258@seu.edu.cn
* Correspondence: wenyong_9731@126.com

Abstract: The toughening modification of epoxy resin by polyurethane prepolymer (PU) can ef-
fectively solve the disadvantage of high brittleness in its application. In this study, a convenient
way to toughen epoxy resins was explored, and the monomers PPG and MDI for the synthesis of
polyurethane prepolymers were used for a one-step modification of epoxy resins. The test results
of viscosity and elongation at break showed that P-M reduced the viscosity of the epoxy resin and
improved the toughness. Especially when the content of P-M was 25%, the elongation at the break of
the modified EP reached 196.56%. From a thermogravimetric and pyrolysis kinetic analysis, the P-M
modification had better thermal stability than the PU modification. These findings have particular
implications for the toughening and engineering applications of epoxy resins.

Keywords: epoxy resin; modified; viscosity; thermal decomposition; kinetic

1. Introduction
Epoxy resin (EP) has been widely used in coatings, adhesives, aviation, construc-
Citation: Wen, Y.; Liu, X.; Liu, L.
tion materials, composite materials, and photoelectric materials, due to its high bonding
Improving Epoxy Resin Performance
strength, mechanical strength, excellent chemical resistance, electrical insulation, and di-
Using PPG and MDI by One-Step
mensional stability [1–5]. However, the shortcomings of epoxy resin such as high brittleness
Modification. Processes 2022, 10, 929.
and easy cracking also greatly limit its application in the industrial field. The low toughness
https://doi.org/10.3390/pr10050929
and poor crack resistance of EP caused by highly cross-linked structures has always been a
Academic Editor: Chi-Min Shu problem and research direction for scholars to solve [6,7]. Consequently, many efforts have
Received: 21 February 2022
been focused on improving the toughness of EP in recent years.
Accepted: 3 May 2022
In order to improve the toughness of EP, second components such as nanoparti-
Published: 7 May 2022
cles [8,9], fibers [10,11], and polymers [12,13] are used as toughening modifiers or even
composite modification. Yang et al. [8] used the prepared regenerated cellulose and nano-
Publisher’s Note: MDPI stays neutral
carbon dioxide hybrid material as a modifier to increase the tensile strength and impact
with regard to jurisdictional claims in
toughness of epoxy resin by 38% and 40%, respectively. Wang et al. [7] used liquid γ-
published maps and institutional affil-
aminopropyl triethoxysilane (APTES)-modified Sm2O3 nanoparticles to improve the me-
iations.
chanical properties of epoxy resins, and the peak elongation at break of the composite was
only 0.68%. Although the modification of epoxy resin by nanomaterials can improve its
flexibility to a certain extent, the problems of dispersion of nanoparticles in epoxy resin
Copyright: © 2022 by the authors.
and interfacial incompatibility have not been solved. On the other hand, the uneconomical
Licensee MDPI, Basel, Switzerland. nature of nanoparticles also precludes them from being widely used in engineering.
This article is an open access article Polymers are also often used to improve the toughness of epoxy resins, [14] of which
distributed under the terms and polyurethanes have been widely studied due to their good flexibility [15]. Since Frisch
conditions of the Creative Commons first reported polyurethane (PU)-modified EP [16], many related works have been widely
Attribution (CC BY) license (https:// studied due to the superior flexibility and excellent mechanical properties of interpen-
creativecommons.org/licenses/by/ etrating network polymers (IPNs) [17,18]. Bakar and Kostrzewa synthesized PUs with
4.0/). different isocyanates and polyols and discussed the effect of PU types on the toughness of

Processes 2022, 10, 929. https://doi.org/10.3390/pr10050929 https://www.mdpi.com/journal/processes

Processes 2022, 10, 929 2 of 11

EP. Experiment results indicated that an IPN was formed through a graft reaction between
the isocyanate-terminated PU and EP, greatly improving the toughness and reducing the
glass transition temperature of the EP [19–23]. Li’s research results showed that there
was a graft reaction between the polymer network I formed by epoxy resin with a curing
agent and polymer network II obtained via PUP reactions with a chain extender and cross-
linker [24–26]. Dharmalingam Sivanesan et al. prepared polycaprolactone polyols with
different molecular weights and chain lengths, and then prepared polyurethane-modified
epoxy resins with hexamethylene diisocyanate. The results showed that the addition of
polyurethanes and EP formed cross-linking bonds, thereby increasing the tensile strength
from 63 MPa to 81 MPa [27]. Studies by many scholars have proved that due to the cross-
linking effect of polyurethane and EP, the phenomenon of phase separation is avoided in
the system, thereby improving the mechanical properties.
In previous studies, the modification of EP usually required two stages, namely the
preparation of polyurethane and the blending with epoxy resin. In this paper, the steps
of preparing the polymer were omitted. Moreover, the research on the toughening and
modification of epoxy resin by PPG and MDI, the monomer for preparing the polyurethane
prepolymer, has rarely been reported. In this study, epoxy resin was modified with MDI
and PPG, compared with the traditional polyurethane prepolymer modification, and the
effect of the modifier addition on the mechanical properties of epoxy resin was discussed.
In addition, the viscosity, initial setting time, and thermal stability of the modified epoxy
resin were also discussed in this study; the thermal decomposition kinetic parameters were
analyzed by Kissinger and Flynn–Wall–Ozawa (F–W–O) methods, respectively.

2. Experimental Section
2.1. Materials
4,40-Diphenylmethane diisocyanate (MDI) and polypropylene glycol (PPG Mw = 1000 g mol−1)
were supplied by Jining Baiyi Chemical Co. (Shandong, China). PPG was an industrial prod-
uct that was dehydrated under a vacuum at 120 ◦ C for 2 h before use. Epoxy resin (EP), with
an epoxy value of 0.51 mol/100 g, was purchased from Guangzhou Qian Chemical Co., Ltd.
(Guangzhou, China). The curing agent (model 421, amine value was 380 ± 20 mg KOH/g)
was obtained from Boyu Biological Engineering Co., Ltd. (Shandong, China).

2.2. Preparation of Polyurethane Prepolymer

Under vacuum conditions, the PPG was added dropwise into the preweighed MDI
using a peristaltic pump at a speed of 30 r/min (n (NCO): n (OH) = 1.5). Then, the reaction
temperature was kept at 70 ◦ C for 3.5 h and it yielded PUP. The viscosity of the PUP sample
was 13,400 mPa·s, and the isocyanate content measured by the di-n-butylamine back drop
method is 2.96%.

2.3. Preparation of Modified Epoxy Resin

EP, modified with different contents of PPG and MDI (n (NCO): n (OH) = 1.5), 0, 10,
20, 25, and 30 wt %, was prepared. First, PPG and MDI were added into EP and stirred
at room temperature for 15 min. Then, the curing agent (33 wt % of EP) was added and
stirred for 15 min. The mixture was poured into a mold coated with vacuum silicone grease
and placed in a vacuum oven at 80 ◦ C for 2 h to remove air bubbles. Next, it was demolded
after curing for 24 h at room temperature, and the obtained materials were denoted as
E-(P-M X%), where X was the amount of PPG and MDI.
For comparison, PPG and MDI in the above system were replaced with the as-
synthesized PUP, and the other conditions were the same as the above procedure, leading
to the PUP-modified EP with 0, 10, 20 25 and 30 wt %, which is designated as E-(PUP X%).
The specific steps of sample preparation were shown in Figure 1.
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Figure 1.
Figure Preparation of
1. Preparation ofsamples.
samples.
2.4. Testing Methods
2.4. Testing Methods
The VERTEX 70 (Brook, Germany) was used for the Fourier transform infrared spec-
The VERTEX
troscopy (FT-IR) to70test(Brook, Germany)
the sample waswith
structure usedIRfor the Fourier
spectra from 400 transform
to 4000 cm infrared
−1 . spec-
troscopy (FT-IR) to test the sample structure with IR spectra from 400
The viscosity test of the sample was carried out according to GB/T 2974-2013, using to 4000 cm −1.

The viscosity
the NDJ-1F testviscometer
rotational of the sample was carried
of Shanghai ChangjioutGeological
accordingInstrument
to GB/T 2974-2013,
Co., Ltd., theusing
the NDJ-1F
rotor rotational
model was no. 29,viscometer
and the speed of was
Shanghai Changji
10 r/min. Geological
The time from when Instrument
the sample Co.,
wasLtd.,
the rotor model
measured to whenwasthe no.viscosity
29, and reached
the speed was mpa
60,000 ·s wasThe
10 r/min. time as
selected fromthewhen
initialthe sample
setting
time.measured
was We took the average
to when value
the of three
viscosity parallel60,000
reached experiments for each
mpa·s was sample.
selected as the initial set-
The tensile
ting time. We took strength and elongation
the average at break
value of three were experiments
parallel tested on the forFR-100C electronic
each sample.
universal testing machine (Farui, China) according to the GB/T 2567-2008
The tensile strength and elongation at break were tested on the FR-100C electronic standard, and
the tensiletesting
universal rate was 2 mm/min
machine until
(Farui, the samples
China) according broke.
to theThe values
GB/T of tensile
2567-2008 strengthand
standard,
and elongation at break were the average values of 3 samples. The tensile
the tensile rate was 2 mm/min until the samples broke. The values of tensile strength strength of theand
sample was calculated as Equation (1):
elongation at break were the average values of 3 samples. The tensile strength of the sam-
ple was calculated as Equation (1): F
σt = (1)
b × hF
σ = (1)
b sample
In the formula, σt is the tensile strength of the h (MPa); F is the maximum load
that In
thethe
sample bears
formula, σt(N); b is
is the the width
tensile of the
strength sample
of the (mm);
sample h is Fthe
(MPa); is thickness of theload
the maximum
sample
that the(mm).
sample bears (N); b is the width of the sample (mm); h is the thickness of the
sample The(mm).
elongation at break of the sample was calculated Equation (2):
The elongation at break of the sample ∆L was calculated Equation (2):
e= × 100% (2)
L0 ΔL
e= 100% (2)
L
where e is the elongation at break; L0 is the gauge length of the sample (mm); ∆L is the
gauge length
where e is theelongation
elongationat at
break (mm).
break; L0 is the gauge length of the sample (mm); ΔL is the
gaugeAdditionally, the tensile
length elongation strength
at break (mm).and elongation at break were tested on the FR-
100CAdditionally,
electronic universal testing
the tensile machine
strength (Farui, China)
and elongation according
at break to the on
were tested GB/T 2567-
the FR-100C
2008 standard. Thermal
electronic universal testing stability was monitored on an STA 7300 (Hitachi, Japan)
machine (Farui, China) according to the GB/T 2567-2008 from
stand-
room temperature to 600 ◦ C, with heating rates of 5, 10, 15, 20 and 25 ◦ C/min under a
ard. Thermal stability was monitored on an STA 7300 (Hitachi, Japan) from room temper-
nitrogen atmosphere.
ature to 600 °C, with heating rates of 5, 10, 15, 20 and 25 °C/min under a nitrogen atmos-
phere.
2.5. Kinetic Analysis of Thermal Decomposition
The thermal degradation process of EP can be expressed as Equation (3) when only
2.5. Kinetic Analysis of Thermal Decomposition
considering whole chemical changes:
The thermal degradation process of EP can be expressed as Equation (3) when only
A(s) → B(s) + C(g)
considering whole chemical changes: (3)

The conversion rate is defined asA(s) → B(s)+C(g)

Equation (4): (3)
m − m(4):
The conversion rate is defined asα Equation t
= 0 (4)
m0 − m1
m0 − mt
where m0 and m1 are the initial mass ofαthe = sample and the final mass after reaction, (4)
0 − m1 at time t.
respectively, and mt represents the mass of themsample
where m0 and m1 are the initial mass of the sample and the final mass after reaction, re-
spectively, and mt represents the mass of the sample at time t.
The decomposition rate dα/dt is a function of the conversion rate α and temperature T, as
Equation (5):
Processes 2022, 10, 929 4 of 11

The decomposition rate dα/dt is a function of the conversion rate α and temperature
T, as Equation (5):
dα
= k( T ) f (α) (5)
dt
where k is the reaction rate constant. This term is a function of temperature T and can be
expressed by the Arrhenius formula, as Equation (6):

Ea
k = A exp(− ) (6)
RT

where A is the frequency factor (s−1 ), Ea is the activation energy of the decomposition
reaction (KJ mol−1 ), R is the general gas constant (R = 8.314 J mol−1 K−1 ), and T is the
reaction temperature (K).
Substituting Equations (6) and (5), we obtain Equation (7):

dα Ea
= A exp(− ) f (α) (7)
dt RT
For a constant heat rate β = dT/dt thermal degradation system, the kinetic parameters
can be obtained from the overall rate equation, as Equation (8):

dα A Ea
= exp(− ) f (α) (8)
dT β RT

Several methods of calculating kinetic parameters can be obtained through various

deductions of Equation (8). In this paper, we calculated the kinetic parameters of the
modified EP by adopting the classic Kissinger (Equation (9)) and Flynn–Wall–Ozawa
(Equation (10)) equations [28,29]. The advantage of the Kissinger method is that Ea can be
obtained without understanding the thermal degradation reaction mechanism. Moreover,
the Flynn–Wall–Ozawa (F–W–O) method is also known as the integral method, and it is very
suitable for explaining the kinetic parameters under complex thermal degradation reactions.

β Ea AR
ln( )=− + ln (9)
Tp2 RTp Ea

AEa Ea
ln( β) = lg − 2.315 − 0.4567 (10)
RG (α) RT

3. Results and Discussion

3.1. FT-IR of P-M-Modified Epoxy Resin
Figure 2 presents the FT-IR spectra of modifying agents and E-(P-M X%). The char-
acteristic peaks at 3400 and 913 cm−1 are stretching vibrations of the hydroxyl and epoxy
groups in the EP, respectively, and peaks at 2271 and 1523 cm−1 are stretching vibrations of
the N=C=O groups and the benzene rings in the MDI. The vibrational peaks of C–O–C and
–OH in the PPG are at 1108 and 3475 cm−1 , respectively. In the PUP, the characteristic peaks
at 2271 and 1735 cm−1 are NCO and urethane groups, respectively.
In the infrared spectra of E-(P-M X%), it can be clearly seen that the N=C=O charac-
teristic peak near 2270 cm−1 in the MDI disappears, and a new characteristic peak that
belongs to C=O in carbamate appears near 1730 cm− 1 . The disappearance of the N=C=O
groups may be due to the reaction with a curing agent containing more reactive amino
groups (Equation (11)). The IR results prove that during the E-(P-M X%), PPG and MDI
reacted to form carbamate, and a part of the MDI was consumed by the curing agent.
Processes 2022, 10,2022,
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929 REVIEW 5 of 11 5 of 11

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PUP E_(P_M 30%)

PUP E_(P_M 30%) 25%)
E_(P_M
EP E_(P_M 25%)20%)
E_(P_M
EP E_(P_M 20%)
MDI E_(P_M 10%)
MDI E_(P_M 10%)

PPG
PPG
E_(P_M
E_(P_M 0%) 0%)

4000
4000 3000
3000 2000
2000 1000 1000 400040003000 3000
2000 2000 1000 1000
-1 -1 -1
Wavenumber (cm
Wavenumber (cm ) ) Wavenumber (cm )
Wavenumber (cm-1)
(a) (b)
(a) (b)
Figure 2. FT-IR spectra of modifying agents and E-(P-M X%). (a) Modifiers and pure EP, (b) Modi-
Figure 2. FT-IR
fied Figure
Epoxy 2. spectra
FT-IR
Resin. spectraofofmodifying agents
modifying agents and
and E-(P-M
E-(P-M X%).X%). (a) Modifiers
(a) Modifiers and pureand
EP, pure EP, (b) Modi-
(b) Modified
fied Epoxy
EpoxyResin.
Resin.

(11)
(11) (11)

3.2. 3.2. Properties

Properties of Modified
of Modified Epoxy Epoxy
Resin Resin
TheThe viscosity
viscosity of EP of has
EP has a significant
a significant effecteffect
on itsonprocessing
its processing ability
ability andand the properties
the properties
3.2. Properties of Modified
samples. The Epoxy
lower Resin
of cured samples. The lower viscosity facilitates operability during later construction [30].[30].
of cured viscosity facilitates operability during later construction
Figure
FigureThe 3 shows
viscosity
3 shows thethe ofviscosity
EP has
viscosity and aand initial
significant
initial setting
setting timeresults
effect
time onresults forthe
thePUP-M
its processing
for PUP-M andP-M
ability
and P-M samples.
andsam-the properties
ples.In the
In the viscosity test,
viscosityThe two
test,lower extremes
two extremes can be seen, the viscosity of the PUP-M sample increases
of cured samples. viscositycan be seen, the
facilitates viscosity of
operability the PUP-M
during sample
later construction [30].
sharply with the increase of the amount of this modifier, because the prepared PUP itself
increases
Figure sharply with the increase of the amount of this modifier, because the prepared
has 3a shows the viscosity
higher viscosity due to andits initial setting time
larger molecular weight.results Thefor the resin
epoxy PUP-M and
itself hasP-M
a sam-
PUP itself has a higher viscosity due to its larger molecular weight. The epoxy resin itself
ples. large viscosity base, so it shows a viscosity trend, while the PPG and MDI monomers sample
In the viscosity test, two extremes can be seen, the viscosity of the PUP-M
has a large viscosity base, so it shows a viscosity trend, while the PPG and MDI monomers
increases
Processes 2022, 10, x FOR PEER REVIEW sharply
as modifiers arewith
just thetheopposite,
increasebecauseof the PPGamount and MDI
as modifiers are just the opposite, because PPG and MDI as monomers have a very low
of this modifier, have
as monomers becausea verythelow
prepared
6 of 11
PUP viscosity.
itself hasAdding
a higherit to the epoxy
viscosity resin
due acts
to as
its a diluent
larger to a
molecular certain extent,
weight. so the
The higher
epoxy the
resin itself
viscosity. Adding it to the epoxy resin acts as a diluent to a certain extent, so the higher
has aamount
large of monomer
viscosity base,added, so the
it lowerathe
shows viscositytrend,
viscosity of the while
system.the PPG and MDI monomers
the amount of monomer added, the lower the viscosity of the system.
as modifiers
Notably, are just the
the initial opposite,
setting time of because PPG and
the two modified EPs MDI first as monomers
increases and then havede-a very low
50 E-(PUP butX%)
viscosity. Adding it to the epoxy resin acts as a diluent to a certain extent, the
creases, the reason for this trend is different. With the increase in P-M content, so the higher
theE-(P-M
active NCO
amount X%)group
of monomerincreases, the reaction
added, becomes
the lower the more
viscosityintense, andsystem.
of the the viscosity rises
40
Viscosity (Pa·s)

faster, so the initial setting time is short, while the initial viscosity of the PUP modification
Notably, the initial setting time of the two modified EPs first increases and then de-
system increases with the rise in PUP content. When the PUP content is 30%, the initial
30 creases,
viscositybut of thethe reason
system for this
is 43,274 trend
mPa·s, whichis different.
dramatically With the increase
shortens the time for in the
P-M content, the
sys-
active NCO group increases, the reaction becomes more
tem’s viscosity to reach 60,000 mPa·s (i.e., the initial setting time). At the same dosage, the intense, and the viscosity rises
20 faster, so the time
initial setting initialof setting
the P-M time is short,iswhile
modification alwaysthe initial
slightly viscosity
higher of the
than that PUP
of the modification
PUP.
system increases
In practice, this means with thatthe therise
P-Minmodification
PUP content. When
provides the PUP
a longer contenttime.
operational is 30%, the initial
10
viscosity of the system is 43,274 mPa·s, which dramatically shortens themodifi-
In conclusion, the viscosity of the system can be greatly reduced during the time for the sys-
cationviscosity
of P-M, and the operating time estimated from the setting
initial setting time can same
also bedosage, the
0 tem’s to reach 60,000 mPa·s (i.e., the initial time). At the
0% adjusted
10% by 20% 25% of30%
the amount P-M added.
initial setting time of the P-M modification is always slightly higher than that of the PUP.
Contents
In practice, this means that the P-M modification provides a longer operational time.
(a)
In conclusion, the viscosity of the system can (b)be greatly reduced during the modifi-
cation 3.ofViscosity
Figure P-M, and and the operating time
initial time estimated from the initial setting timesetting
can also be
Figure 3. Viscosity and initialsetting
setting time ofofthe
the modified
modified EP.Viscosity,
EP. (a) (a) Viscosity, (b)setting
(b) initial initialtime. time.
adjusted by the amount of P-M added.
Figure 4 represents the tensile strength and elongation at break of the PUP-M and P-
M samples. The tensile strength showed a decreasing trend in both modified samples, but
the mechanism was different. In the process of the P-M modification, an infrared analysis
revealed that the MDI also consumed part of the curing agent 421 when the PPG reacted
 Figure 3. Viscosity and initial setting time of the modified EP. (a) Viscosity, (b) initial setting time.

Figure 4 represents the tensile strength and elongation at break of the PUP-M and P-
Processes 2022, 10, 929
M samples. The tensile strength showed a decreasing trend in both modified samples, 6 of 11
but
the mechanism was different. In the process of the P-M modification, an infrared analysis
revealed that the MDI also consumed part of the curing agent 421 when the PPG reacted
to generate PUP, the
Notably, which resulted
initial setting in theofincomplete
time curingEPs
the two modified of the EPincreases
first itself whenand the
thenamount
of modifier
decreases, wasbuttoo high. However,
the reason for this trend a decrease
is different.inWith
tensile strengthinof
the increase P-Mthecontent,
PUP-M thesamples
has active NCO group
been reported inincreases, the reaction
the literature due to becomes more intense,
the formation and the viscosity
of alkanone rises by the
structures
epoxyfaster, so thein
groups initial
PUPsetting
and time is short,
EP with NCO while endthe groups,
initial viscosity of the PUP
[31] which led modification
to the decrease in
system increases with the rise in PUP content. When the PUP content is 30%, the initial
tensile strength.
viscosity of the system is 43,274 mPa·s, which dramatically shortens the time for the
The P-M
system’s modification
viscosity showed
to reach 60,000 mPaa·slarger elongation
(i.e., the initial settingat time).
break,Atand for (EP-P-M
the same dosage, 25%),
the elongation at break
the initial setting time achieved
of the P-Mamodification
maximum isofalways 196.56%. It can
slightly be clearly
higher than that seen that both
of the
modification methods
PUP. In practice, can improve
this means the modification
that the P-M elongation at the break
provides of EP
a longer to a certain
operational time. extent.
In conclusion,
This is because the viscosity
both modifiers of the system
contain can be greatly
the generated PUP,reduced
and PPG during
as athe modifi-
flexible segment
cation of P-M, and the operating time estimated from the initial
in PUP can improve the sample’s flexibility, which has been reported in many papers [32]. setting time can also be
adjusted by the amount of P-M added.
The elongation at the break of P-M was higher than that of PUP. During the modifica-
Figure 4 represents the tensile strength and elongation at break of the PUP-M and
tion P-M
process of P-M,
samples. The the curing
tensile agent
strength 421 consumed
showed a decreasinga trend
part of the MDI,
in both modifiedwhich caused free
samples,
PPGbutto form a continuous
the mechanism collision polymer
was different. In the process due of
to the
the P-M
dehydration
modification,andan condensation
infrared of
a gunshot
analysisduring
revealedthethatcuring
the MDIprocess of EP. The
also consumed partresult
of theof the infrared
curing agent 421 analysis
when the confirmed
PPG
reacted to generate PUP, which resulted in the incomplete curing
this conjecture. Obviously, the chain polymer of free PPG dehydration–condensation of the EP itself when the in
amount of modifier was too high. However, a decrease in tensile
the system is beneficial to the flexibility of the system. With the increase of P-M content,strength of the PUP-M
samples has been reported in the literature due to the formation of alkanone structures by
the late resin hardly has any strength, so the elongation at break shows a decreasing
the epoxy groups in PUP and EP with NCO end groups, [31] which led to the decrease in
trend at that
tensile time.
strength.

225
200 E-(PUP X%)
Elongation at break (%)

E-(P-M X%)
175
150
125
100
75
50
25
0
0% 10% 20% 25% 30%
Contents
(a) (b)
Figure 4. Tensile
Figure strength
4. Tensile strengthand
and elongation
elongation atat break
break of the
of the modified
modified EP. (a)EP. (a) Tensile
Tensile strength,strength,
(b) elonga-(b)
elongation at break.
tion at break.

The P-M modification showed a larger elongation at break, and for (EP-P-M 25%),
the elongation at break achieved a maximum of 196.56%. It can be clearly seen that both
modification methods can improve the elongation at the break of EP to a certain extent.
This is because both modifiers contain the generated PUP, and PPG as a flexible segment in
PUP can improve the sample’s flexibility, which has been reported in many papers [32].
The elongation at the break of P-M was higher than that of PUP. During the modifica-
tion process of P-M, the curing agent 421 consumed a part of the MDI, which caused free
PPG to form a continuous collision polymer due to the dehydration and condensation of
a gunshot during the curing process of EP. The result of the infrared analysis confirmed
this conjecture. Obviously, the chain polymer of free PPG dehydration–condensation in the
system is beneficial to the flexibility of the system. With the increase of P-M content, the
late resin hardly has any strength, so the elongation at break shows a decreasing trend at
that time.
Processes 2022, 10, x FOR PEER REVIEW 7 of 11
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3.3.3.3.
Thermal
ThermalProperties
Properties
Figure 5 displays
Figure 5 displays thethe
TG (weight
TG (weightloss)
loss)and
andDTGDTG(weight
(weightderivative)
derivative)curves
curvesofofEP-(P-
EP-(P-M
M X%)
X%) andand EP-(PUP X%). The initial decomposition temperature
EP-(PUP X%). The initial decomposition temperature (Ti) of unmodified (Ti) of unmodified EPEP is is
325.96 °C,◦ and the weight loss reached a maximum at 368.83 °C.
325.96 C, and the weight loss reached a maximum at 368.83 C. EP-(PUP X%) slightly ◦ EP-(PUP X%) slightly
reduces
reduces thethe
initial decomposition
initial decomposition temperature
temperature of EP,
of EP,while EP-(P-M
while EP-(P-M X%)X%)obviously
obviouslyhashasa a
higher
higher Ti Ti
than
than EP-(PUP
EP-(PUP X%), which
X%), which indicates
indicates thatthatEP-(P-M
EP-(P-M X%)X%)modification
modification makes
makes thethe
polymer
polymer have
havehigher
higher crosslinking
crosslinkingdensity,
density,which
whichisisattributed
attributed to
to the MDI in the
the modification
modifica-
tion process
process notonly
not onlyreacted
reactedwith
withPPG
PPG to to form PUP PUP but butalso
alsografted
graftedinto
intoEPEPthrough
through thethe
reaction with curing agent. EP-(PUP X%) exhibits lower thermal
reaction with curing agent. EP-(PUP X%) exhibits lower thermal stability mainly due stability mainly due to to
thethe
presence of more relatively weak urethane linkages in the system [33].
presence of more relatively weak urethane linkages in the system [33]. However, this However, this
phenomenon
phenomenon of of
reduced
reduced thermal stability
thermal stabilitywas notnot
was found
foundin the P-M
in the modification
P-M modificationprocess,
process,
because
because in in
addition
addition to to
thethe
grafting of PUP
grafting of PUP to EP,
to EP, there
therewas also
was a part
also of of
a part MDIMDIto to
EPEPto to
form
form oxazolidinones.
oxazolidinones.

100% (a) 100% (b)

80% 80%

Weight (%)
Weight (%)

60% 60%
E_(PUP 0%) E_(P_M 0%)
40% E_(PUP 10%) 40% E_(P_M 10%)
E_(PUP 20%) E_(P_M 20%)
20% 20% E_(P_M 25%)
E_(PUP 25%)
0% E_(PUP 30%) 0% E_(P_M 30%)

-100 0 100 200 300 400 500 600 -100 0 100 200 300 400 500 600
Temperature (℃) Temperature (℃)
Deriv.Weight ( wt %/min)
Deriv.Weight ( wt %/min)

E_(PUP 0%) (c) E_(P_M 0%) (d)

30% 30%
E_(PUP 10%) E_(P_M 10%)
E_(PUP 20%) E_(P_M 20%)
20% E_(PUP 25%) 20% E_(P_M 25%)
E_(PUP 30%) E_(P_M 30%)
10% 10%

0%
0%
-100 0 100 200 300 400 500 600 -100 0 100 200 300 400 500 600
Temperature (℃) Temperature (℃)

Figure
Figure 5. TG
5. TG andand
DTGDTG of the
of the modified
modified EP.EP.
(a) (a)
TG TG of PUP
of PUP modified
modified EP, EP,
(b) (b)
TG TG of P-M
of P-M modified
modified EP, EP,
(c) (c)
DTGDTG of PUP
of PUP modified
modified EP,EP,
(d)(d)
DTGDTG
of of
P-M P-M modified
modified EP.
EP.

3.4. Thermal Decomposition Kinetic

3.4. Thermal Decomposition Kinetic
Kissinger Method
Kissinger Method
For the Kissinger method, Ea was determined by the slope of the linear fit of ln
For thetoKissinger
(β/Tp2) 1/Tp withmethod,
varyingEa P-M was determined
contents (Figure by6).theTheslope of the
thermal linear fit of
degradation ln
kinetic
(β/Tp2) to 1/Tp with varying P-M contents (Figure 6). The thermal degradation
parameters are listed in Table 1. Consequently, there was a linear relationship for different kinetic
parameters are listed
P-M contents, in Table
signifying the1.reliability
Consequently,of thethere was amethod
Kissinger linear relationship for different
under this system. The Ea
P-M contents,
value of the signifying
unmodifiedthe EPreliability
was 58.97of KJthe
·mol Kissinger
−1 ; E-(P-Mmethod
20%) and under this system.
E-(P-M The Ea by
25%) increased
value ofKJ
11.32 the unmodified
·mol −1 and 6.47EP KJwas
·mol58.97 KJ·mol−1; E-(P-M
−1 , respectively, compared 20%) to and E-(P-M 25%)
the unmodified EP,increased
suggesting
bythat
11.32 KJ·mol −1 and 6.47 KJ·mol −1, respectively, compared to the
the material needs to absorb more heat during thermal degradation, i.e., it has unmodified EP,asug-
higher
gesting thatstability.
thermal the material
The needs
Ea value to absorb moreby
calculated heat during thermal
Kissinger methoddegradation,
was basicallyi.e., it has
consistent
a higher
with thethermal stability.
Ti results shownThe by Ea valuestability,
thermal calculated by Kissinger
which both proved method wasEP-(P-M
that the basicallyX%)
con-had
sistent withthermal
a higher the Ti results shown
stability. When byEa/RT
thermal < stability, which
10, the value both
of Ea proved that
calculated theKissinger
by the EP-(P-
M method
X%) hadisahighly
higherreliable
thermal(i.e.,
stability. When
the error Ea/RT
is less than < 10,
5%)the value of Ea calculated by the
[34].
Kissinger method is highly reliable (i.e., the error is less than 5%) [34].
Processes 2022, 10,
Processes 2022, 10, 929
x FOR PEER REVIEW 8 8of
of 11
11

Figure 6.
6. Relationship
Relationshipbetween
betweenln ln
(β/Tp) andand
(β/Tp) 1/Tp1/Tp
in thermal degradation.
in thermal (a) EP-(P-M
degradation. 0%), (b)0%),
(a) EP-(P-M EP-
(P-M 10%), (c) EP-(P-M 20%), (d) EP-(P-M 25%), (e) EP-(P-M 30%).
(b) EP-(P-M 10%), (c) EP-(P-M 20%), (d) EP-(P-M 25%), (e) EP-(P-M 30%).

Table 1.
Table 1. The
The thermal
thermal degradation
degradation kinetic
kinetic parameters
parameters for
for the
the Kissinger
Kissinger method.
method.

P-M Contents R2 Slope Intercept Ea (KJ·mol−1)

P-M Contents R2 Slope Intercept Ea (KJ·mol−1 )
EP-(P-M 0%) 0.9765 −7093.42 10.49 58.97
EP-(P-M 0%) 0.9765 −7093.42 10.49 58.97
EP-(P-M 10%)
EP-(P-M 10%)
0.9822
0.9822
−5933.12
−5933.12 7.07
7.07
49.33
49.33
EP-(P-M 20%)
EP-(P-M 20%) 0.9960
0.9960 −8454.20
−8454.20 13.86
13.86 70.29
70.29
EP-(P-M
EP-(P-M 25%)
25%) 0.9920
0.9920 −7870.63
−7870.63 12.21
12.21 65.44
65.44
EP-(P-M
EP-(P-M30%)
30%) 0.9392
0.9392 −5211.02
−5211.02 4.94
4.94 43.32
43.32

For the F–W–O method, Ea was determined by the slope of the linear fit of lg β to
1/Tppwith
1/T withdifferent
differentP-M
P-Mcontents
contents (Figure
(Figure 7). Unlike
Unlike the
the Kissinger
Kissinger method, Eaa of the thermal
degradation
degradation system
system at ateach
eachmoment
momentcan canbebe calculated
calculated directly. In this
directly. paper,
In this Ea was
paper, cal-
Ea was
culated
calculatedwith a 10
with to to
a 10 80%
80% conversion
conversionraterate(increments
(incrementsofof10%),
10%),and
andthe theresults
results are
are shown
Table 2. Eaa was
in Table was highly
highly dependent
dependent on on the
the conversion
conversion rate
rate due
due to
to the
the multistage
multistage reactivity
reactivity
of the
the modified
modifiedEP EPduring
during thermal
thermal degradation
degradation [26].
[26]. Moreover,
Moreover, Ea gradually
Ea gradually increased
increased from
low tolow
from high
to conversion because
high conversion the degradation
because reactions
the degradation occurred
reactions at various
occurred stagesstages
at various in the
thermal
in degradation
the thermal process.
degradation The initial
process. stage was
The initial stageprimarily involved
was primarily in the evaporation
involved in the evap-
of water,ofsowater,
oration Ea wasso low.
Ea was low.
The Ea obtained by the F–W–O method did not differ much from that of the Kissinger
Table
method 2. F–W–O
becausemethod to calculate
the Kissinger the thermal
method doesdegradation
not involve kinetic parameters. rate during the
the conversion
degradation process. The thermal degradation kinetic parameters obtained by the two
Ea (KJ·mol−1 )
methods
α proved that the P-M modification did not significantly reduce the material’s ther-
EP-(P-M 0%)
mal stability like the PUPEP-(P-M 10%)
modification. EP-(P-M 20%) EP-(P-M 25%) EP-(P-M 30%)
10% 42.92 49.09 50.81 41.90 34.44
20% 51.34 51.43 57.83 56.73 52.05
30% 56.03 52.45 57.85 59.37 55.58
40% 57.58 53.84 58.06 61.46 57.11
50% 58.48 55.79 58.64 58.58 57.38
60% 59.97 56.61 58.89 58.01 57.81
70% 62.54 59.51 62.06 60.08 59.93
80% 67.34 63.51 66.21 63.24 63.32
Average 57.03 55.28 58.79 57.42 54.70

The Ea obtained by the F–W–O method did not differ much from that of the Kissinger
method because the Kissinger method does not involve the conversion rate during the
degradation process. The thermal degradation kinetic parameters obtained by the two
methods proved that the P-M modification did not significantly reduce the material’s
thermal stability like the PUP modification.
 in the thermal degradation process. The initial stage was primarily involved in the evap-
oration of water, so Ea was low.
The Ea obtained by the F–W–O method did not differ much from that of the Kissinger
method because the Kissinger method does not involve the conversion rate during the
degradation process. The thermal degradation kinetic parameters obtained by the two
Processes 2022, 10, 929 9 of 11
methods proved that the P-M modification did not significantly reduce the material’s ther-
mal stability like the PUP modification.

Processes 2022, 10, x FOR PEER REVIEW 9 of 11

Figure 7. Relationship
Figure between
7. Relationship lgβlgβ
between andand
1/Tp in thermal
1/Tp degradation.
in thermal (a) EP-(P-M
degradation. 0%),0%),
(a) EP-(P-M (b) (b)
EP-(P-M
EP-(P-M
10%), (c) EP-(P-M 20%), (d) EP-(P-M 25%), (e) EP-(P-M 30%).
10%), (c) EP-(P-M 20%), (d) EP-(P-M 25%), (e) EP-(P-M 30%).

Table 2. F–W–O method to calculate the thermal degradation kinetic parameters.

4. Conclusions and Future Work
Ea (KJ·mol
This study laid a theoretical foundation −1)
for the facile preparation of EP with good
α
flexibility. The modification
EP-(P-M 0%) EP-(P-M of 10%)
EP withEP-(P-M
MDI and20%)PPG was used to
EP-(P-M compare
25%) with30%)
EP-(P-M conven-
tional
10% PUP modification.
42.92 Due to
49.09 the low viscosity
50.81 of the added monomer,
41.90 which
34.44 acts as a
diluent
20% in the system,
51.34 the viscosity
51.43 was obviously
57.83 reduced from 7820
56.73 mPa · S to 1034
52.05 mPa ·S.
Interestingly,
30% as the monomer
56.03 content increased,
52.45 57.85 the highly reactive
59.37 NCO group 55.58increased.
The increase of the group made the viscosity of the system rise sharply in the later stage.
40% 57.58 53.84 58.06 61.46 57.11
The one-step modification of EP by MDI and PPG greatly improved the flexibility, and a
50% 58.48 55.79 58.64 58.58 57.38
maximum value of 196.56% was obtained when the dosage was 25%. This indicated that
60% 59.97 56.61 58.89 58.01 57.81
both modification methods reduced the tensile strength. In addition, the thermogravimetric
70%
test and thermal degradation kinetics results both proved that the one-step59.93
62.54 59.51 62.06 60.08 modified EP
80% 67.34 stability.
had better thermal 63.51 66.21 63.24 63.32
AverageThis kind57.03 55.28a good flexibility
of P-M-EP with 58.79has great application
57.42 prospects 54.70
in industry,
such as road repair materials and concrete crack repair. Of course, the application perfor-
4. Conclusions and Future
mance in practical Work such as the ability to repair cracks, will be systematically
engineering,
reported in follow-up
This study studies. foundation for the facile preparation of EP with good
laid a theoretical
flexibility. The modification of EP with MDI and PPG was used to compare with conven-
tional PUP modification. Due to the low viscosity of the added monomer, which acts as a
diluent in the system, the viscosity was obviously reduced from 7820 mPa·S to 1034 mPa·S.
Interestingly, as the monomer content increased, the highly reactive NCO group in-
creased. The increase of the group made the viscosity of the system rise sharply in the
Processes 2022, 10, 929 10 of 11

Author Contributions: Conceptualization, Y.W.; methodology, Y.W.; software, Y.W.; validation, Y.W.
and L.L.; formal analysis, X.L.; investigation, X.L.; resources, Y.W.; data curation, X.L.; writing—
original draft preparation, X.L.; writing—review and editing, L.L.; supervision, Y.W. and L.L.; project
administration, Y.W.; funding acquisition, Y.W. All authors have read and agreed to the published
version of the manuscript.
Funding: This research was funded by the National Natural Science Foundation of China (51768068)
and the TIANSHAN young talent project of Xinjiang (2018Q014).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare that they have no known competing financial interests or
personal relationships that could have appeared to influence the work reported in this paper.

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