coatings

Article
Curing Reaction Kinetics of the EHTPB-Based PBX
Binder System and Its Mechanical Properties
Xing Zhang, Yucun Liu *, Tao Chai, Zhongliang Ma and Kanghui Jia
School of Environment and Safety Engineering, North University of China, Taiyuan 030051, China;
18335161753@163.com (X.Z.); chiao@nuc.edu.cn (T.C.); ma19960512@sohu.com (Z.M.);
j19834405464@163.com (K.J.)
* Correspondence: lycct@nuc.edu.cn




Received: 15 November 2020; Accepted: 16 December 2020; Published: 21 December 2020


Abstract: In this research, differential scanning calorimetry (DSC) was employed to compare the
curing reaction kinetics of the epoxidized hydroxyl terminated polybutadiene-isophorone diisocyanate
(EHTPB-IPDI) and hydroxyl terminated polybutadiene-isophorone diisocyanate (HTPB-IPDI) binder
systems. Glass transition temperature (Tg ) and mechanical properties of the EHTPB-IPDI and HTPB-IPDI
binder systems were determined using the DSC method and a universal testing machine, respectively.
For the EHTPB-IPDI binder system, the change of viscosity during the curing process in the presence of
dibutyltin silicate (DBTDL) and tin 2-ethylhexanoate (TECH) catalysts was studied, and the activation
energy was estimated. The results show that the activation energies (Ea) of the curing reaction of the
EHTPB-IPDI and HTPB-IPDI binder systems are 53.8 and 59.1 kJ·mol−1 , respectively. While their average
initial curing temperatures of the two systems are 178.2 and 189.5 ◦ C, respectively. The EHTPB-IPDI
binder system exhibits a higher reactivity. Compared with the HTPB-IPDI binder system, the Tg of
the EHTPB-IPDI binder system is increased by 5 ◦ C. Its tensile strength and tear strength are increased
by 12% and 17%, respectively, while its elongation at break is reduced by 10%. Epoxy groups and
isocyanates react to form oxazolidinones, thereby improving the mechanical properties and thermal
stability of polyurethane materials. These differences indicate that the EHTPB-IPDI binder system has
better thermal stability and mechanical properties. During the EHTPB-IPDI binder system’s curing
process, the DBTDL catalyst may ensure a higher viscosity growth rate, indicating a better catalytic effect,
consistent with the prediction results obtained using the non-isothermal kinetic analysis method.

Keywords: EHTPB; catalyst; cure kinetics; mechanical properties; DSC

1. Introduction
HTPB-based polyurethane materials have been extensively used as binders for solid composite
propellants and polymer bonded explosives (PBXs) [1,2]. Solid composite propellant is a kind of energetic
composite material with specific performance. It is the power source of a strategic missile, tactical
missile, solid motor of space vehicle and kinetic energy interceptor [3]. Cast PBXs explosive with HTPB
isocyanate system as a binder has the characteristics of good fluidity, long service life, high solid content,
good adhesion with metal, excellent explosion performance and good safety, it has become one of the
main types of solid rocket propellant, large and medium caliber shells, missiles and underwater weapons,
and has been widely used at home and abroad [4,5]. For the traditional HTPB binder system, low polarity,
poor mechanical properties and weak binding strength limit its development in solid propellants. EHTPB
is the introduction of epoxy groups into the molecular chain of hydroxyl-terminated polybutadiene
(HTPB), which can effectively improve the polarity of the molecule, the cured epoxy polymer has good
physical and chemical properties, low shrinkage, high hardness, which can greatly improve the mechanical
properties, and it is used widely for adhesives, sealants, coatings and elastomers [6,7]. EHTPB-based

Coatings 2020, 10, 1266; doi:10.3390/coatings10121266 www.mdpi.com/journal/coatings

Coatings 2020, 10, 1266 2 of 15

polyurethane elastomer exhibits excellent physicochemical properties, making it a promising binder for
solid propellants [8,9]. The kinetic mechanism of the curing reaction reflects the physicochemical properties
of the curing products. Therefore, the polyurethane curing reaction kinetics is of great importance for
designing and producing high-quality products.
Previous research [10–20] of the HTPB curing reaction kinetics focused on the effects of dibutyltin
dilaurate (DBTDL), ferric acetylacetonate (FeAA), triphenyl bismuth (TPB) and tin 2-ethylhexanoate
(TECH) on the HTPB/IPDI binder system. DBTDL exhibited a strong catalyzing effect on the reaction
between isocyanate and alcohols, so-called a gel catalyst. The application of FeAA as a catalyst yielded
a binder system with a relatively short pot life. Cast PBXs explosive and composite solid propellant
are composed of a binder system and solid composition. The catalytic effect of the catalyst TPB on
the HTPB-IPDI binder system is not obvious, and the viscosity of the binder system increases slowly,
which leads to the sedimentation of the solid composition. Compared with DBTDL, TECH is more
environmentally friendly, exhibiting lower toxicity and longer pot life when added into a binder system.
However, to the authors’ best knowledge, research on the EHTPB-based binder system’s curing process
has not been reported so far.
Thermal analysis is one of the most important methods to determine the kinetics of the curing
reaction. Thermogravimetry (TG), differential thermal analysis (DTA) and differential scanning calorimetry
(DSC) have been extensively used to calculate the kinetic parameters [21]. Among these methods, the DSC
method has been the most broadly applied. The curing reaction of the EHTPB-based binder system is
a continuous exothermic process, so the non-isothermal DSC method can be used to study the curing
kinetics of the EHTPB system.
The performance of a polyurethane elastomer relies not only on the chemical composition and
preparation technique but also on the curing conditions. Research on the curing reaction kinetics provides
more in-depth insight into the curing process. This study investigated the curing kinetics of the HTPB-IPDI
and EHTPB-IPDI binder systems using the DSC method. The glass transition temperatures (Tg ) of the
EHTPB-IPDI and HTPB-IPDI polyurethane elastomers were determined. The mechanical properties of
the polyurethane elastomers were tested using a universal testing machine. The curing kinetics of the
EHTPB-IPDI system under different catalytic conditions were studied, and the corresponding curing
kinetic parameters were determined, such as post-processing temperature and curing time in the gelation.
Such as post-processing temperature and curing time in the gelation. These results provide theoretical
support for the determination of the optimal curing parameters.

2. Materials and Methods

2.1. Materials
EHTPB (Mn = 3000 g/mol, the hydroxyl value = 0.75 mmol/g, epoxide value = 0.84 mmol/g and
moisture content = 0.015%) and HTPB (Mn = 3240 g/mol, the hydroxyl value = 0.67 mmol/g and
moisture content = 0.017%) were purchased from Liming Research and Design Institute of Chemical
Industry Co., Ltd., the curing agent, IPDI, from BASF SE (Ludwigshafen, Germany), TECH from
Shanghai Institute of Organic Chemistry (Shanghai, China) and DBTDL from Tianjin Guangfu Fine
Chemical Research Institute (Tianjin, China). EHTPB and HTPB were dried at 100 ◦ C, first in a vacuum,
and then at atmospheric pressure of 0.05 mPa for 4 h before the testing. Subsequently, the dried
chemicals were separately stored in dry and sealed bottles.The chemical structures of the HTPB and
EHTPB are shown in Figures 1 and 2.
A SNB-1A numeric viscosimeter (Shanghai Fangrui Instrument, Shanghai, China) was used to
measure the viscosity of the binder systems, and a DHG303-2 oven (Shanghai Yiheng Instrument,
Shanghai, China) was used to dry the samples. Thermal analysis of the samples was conducted using
an HCT-1 thermal analyzer (Beijing Yongjiu Instrument, Beijing, China).
Coatings 2020, 10, 1266 3 of 15
Coatings 2020, 10, x FOR PEER REVIEW 3 of 17
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Figure 1. Chemical structure of HTPB.

Figure
Figure 1. Chemical structure
1. Chemical structure of
of HTPB.
HTPB.

Figure
Figure 2. Chemical structure
2. Chemical structure of
of EHTPB.
EHTPB.
Figure 2. Chemical structure of EHTPB.
2.2. Sample Preparation
2.2. Sample Preparation
2.2. Sample Preparation
Each binder system was prepared according to the following procedures:
Each binder system was prepared according to the following procedures:
HTPB-IPDI and
Each binder system EHTPB-IPDI
was preparedwithaccording
a weight ratioto theoffollowing
R(nNCO/nOH) = 1 were added into a dry
procedures:
HTPB-IPDI and EHTPB-IPDI with a weight ratio of R(nNCO/nOH) = 1 were added into a dry
beaker. An electrical
HTPB-IPDI andstirring machine
EHTPB-IPDI wasaused
with weight to mix
ratiotheoftwo components for
R(nNCO/nOH) = 1 10 min.
were The pressure
added into a dryof
beaker. An electrical stirring machine was used to mix the two components for 10 min. The pressure
the mixture was reduced to 100 Pa and kept for 5 min to remove the formed bubbles.
beaker. An electrical stirring machine was used to mix the two components for 10 min. The pressure Finally, the binder
of the mixture was reduced to 100 Pa and kept for 5 min to remove the formed bubbles. Finally, the
system was obtained
of the mixture and collected.
was reduced to 100 Pa and kept for 5 min to remove the formed bubbles. Finally, the
binder system was obtained and collected.
binderThe films was
system of the binder and
obtained system were prepared by pouring the as-prepared binder system into
collected.
The films of the binder system were prepared by pouring the as-prepared binder◦ system into
polytetrafluoroethylene (PTFE) molds,
The films of the binder system were placing them in abythermostatic
prepared pouring the oven and curingbinder
as-prepared at 70 C for 7 days.
system into
polytetrafluoroethylene (PTFE) molds, placing them in a thermostatic oven and curing at 70 °C
The thickness of the films is(PTFE)
polytetrafluoroethylene 2 mm. molds, placing them in a thermostatic oven and curing at 70 °C
for 7 days. The thickness of the films is 2 mm.
for 7 days. The thickness of the films is 2 mm.
2.3. Calculation of the Curing Reaction Kinetics
2.3. Calculation of the Curing Reaction Kinetics
2.3. Calculation of the Curing Reaction
Kissinger, Flynn–Wall–Ozawa KineticsDoyle and Crane methods are commonly used to determine
(F-W-O),
Kissinger,
the kinetic Flynn–Wall–Ozawa
parameters (F-W-O),
of a non-isothermal curingDoyle
process. andTheCrane methods
kinetics are commonly
can be expressed used to
by the following
Kissinger, Flynn–Wall–Ozawa (F-W-O), Doyle and Crane methods are commonly used to
determine
equations the kinetic parameters of a non-isothermal curing process. The kinetics can be expressed
determine[22,23]:
the kinetic parameters of a non-isothermal curing process. The kinetics can be expressed
by the following equations [22,23]: d∂
by the following equations [22,23]: = Ae−E/RT × (1 − ∂)n (1)
d∂ dt
Kissinger equation: d ∂ = 𝐴𝑒 / × (1 − 𝜕)/ (1)
d𝑡 = β𝐴𝑒 × (1 − 𝜕) (1)
Kissinger equation:
d𝑡 ln i
= ln (
AR
) −
E 1
· (2)
Tpi 2 E R Tpi
Kissinger equation:
(F-W-O) equation: β" # 𝐴𝑅 𝐸 1
ln β = AEln( 𝐴𝑅) − 𝐸 ∙ 1E (2)
lnln
β = ln = ln(− 𝐸 )− 𝑅 ∙ 𝑇RT
𝑇 Rg(∂) 𝐸 5.330 − 1.0516
𝑅 𝑇
(3)
(2)
𝑇
Doyle equation:
(F-W-O) equation:
(F-W-O) equation:
" #
AE E E
ln β = ln − 2 ln − (4)
𝐴𝐸 Rg(∂) 𝐸 RT RT
lnβ = ln 𝐴𝐸 − 5.330 − 1.0516 𝐸 (3)
Crane equation: lnβ = ln 𝑅𝑔(𝜕) − 5.330 − 1.0516 𝑅𝑇 (3)
𝑅𝑔(𝜕)
d(ln β) E 𝑅𝑇
  =− (5)
Doyle equation: d 1/Tp nR
Doyle equation:
where, Tp and T(K) are the temperatures of 𝐴𝐸 𝐸 is the
the peaks, β (K/min) 𝐸 heating rate, R (8.314 J/mol)
is the gas constant, E (kJ/mol)lnβ = ln
is the 𝐴𝐸
apparent − 2ln
activation 𝐸
energy − 𝐸
and (4)
A is the pre-exponential factor,
lnβ = ln 𝑅𝑔(𝜕) − 2ln 𝑅𝑇 − 𝑅𝑇 (4)
𝑅𝑔(𝜕) and depends
which has the same dimension as the rate constant 𝑅𝑇 on the
𝑅𝑇reaction order, n.
Crane
2.4. DSC equation:
Testing
Crane equation:
d(lnβ)
The DSC tests for the analysis of curing reaction kinetics𝐸were conducted in a nitrogen atmosphere
d(lnβ) − 𝐸 with 10 mg of sample (propellant slurry)
at a flow rate of 50 mL/min. In a typical experiment, a=crucible (5)
d(1/𝑇 ) = − 𝑛𝑅 (5)
d(1/𝑇 ) 𝑛𝑅
2.4. DSC Testing
2.4. DSC Testing
The DSC tests for the analysis of curing reaction kinetics were conducted in a nitrogen
The DSC
atmosphere at atests
flowforratethe analysis
of 50 mL/min. of In
curing reaction
a typical kinetics awere
experiment, conducted
crucible with 10 mg in aofnitrogen
sample
atmosphere at a flow rate of 50 mL/min. In a typical experiment, a crucible
(propellant slurry) was placed in the heating chamber of the DSC analyzer (HCT-1 thermal analyzer, with 10 mg of sample
Coatings 2020, 10, 1266 4 of 15
(propellant
Beijing Yongjiuslurry) was placed
Instrument, in theChina).
Beijing, heatingThe chamber of the DSCwere
measurements analyzer (HCT-1bythermal
performed heatinganalyzer,
from 25
Beijing
to 350 °CYongjiu
at fourInstrument, Beijing,
different heating China).
rates (5, 10,The measurements
15 and 20 °C/min).were performed by heating from 25
was
to 350
The°Cplaced
at fourindifferent
determinationthe heatingTg chamber
ofheating
was rates of(5,
the10,
performed DSC15 analyzer
andthe
using (HCT-1 thermal
20 described
°C/min). analyzer,
DSC tests, except Beijing
that Yongjiu
the heating
Instrument, Beijing, China). The measurements were performed by heating from 25 to 350 ◦ C at four
The determination of T was performed using the described DSC
rate was 10 °C/min. That for Tg the cured◦ samples had been tested by DSC and that an increased
g tests, except that the heating
heat
different heating rates (5, 10, 15 and 20 C/min).
rate was
flow 10 °C/min.behavior)
(endothermic That for Tshows
g the cured
Tg. samples had been tested by DSC and that an increased heat
The determination of Tg was performed using the described DSC tests, except that the heating
flow (endothermic behavior) shows Tg.
rate was 10 ◦ C/min. That for Tg the cured samples had been tested by DSC and that an increased heat
2.5. Mechanical Properties of EHTPB-IPDI and HTPB-IPDI Polyurethane Elastomers
flow (endothermic behavior) shows Tg .
2.5. Mechanical Properties of EHTPB-IPDI and HTPB-IPDI Polyurethane Elastomers
The tensile properties of the EHTPB-IPDI and HTPB-IPDI binder system films were tested with
2.5.
TheMechanical
tensile Properties of
properties of EHTPB-IPDI
the EHTPB-IPDI and HTPB-IPDI Polyurethane Elastomers
an EMT-C universal material testing machine. and HTPB-IPDI binder system films were tested with
an EMT-C
Accordinguniversal
The tensile
to the material
properties
Chineseof testing
standard:machine.
the EHTPB-IPDI and HTPB-IPDI
GB/T 528-1998 binder vulcanized
[24], rubber, system filmsor were tested with we
thermoplastic,
an EMT-C
According
determined universal
the totensile material
the Chinese testing
standard:
stress–strain machine.
GB/T 528-1998
properties. [24], strength
The tensile rubber, vulcanized
and elongationor thermoplastic,
at break of the we
determined According
the to
tensilethe Chinese
stress–strain standard: GB/T
properties. 528-1998
The [24],
tensile rubber,
strength vulcanized
and
specimens were measured by setting the gauge length of the specimens and the tensile speed at 25 or
elongation thermoplastic,
at break of the
we determined the tensile
bystress–strain properties. Theoftensile strength and
specimens
mm and 50were mm/min, measured
respectively.setting
Fivethesamples
gauge length
were cut the specimens
from each typeandofelongation
thebinder
the at break
tensile speedofat
system 25
film,
the specimens were measured by setting the gauge length of the specimens and the tensile speed at
mm further
and and 50 analyzed.
mm/min, respectively. Five samples
Figure 3 represents were cut from each
the dumbbell-shaped type ofThe
specimens. thedata
binder systeminfilm,
recorded the
25 mm and 50 mm/min, respectively. Five samples were cut from each type of the binder system film,
and further analyzed. Figure 3 represents the dumbbell-shaped specimens.
five tests of the same binder system film were collected. The mean value of the indexes obtained The data recorded in the
and further analyzed. Figure 3 represents the dumbbell-shaped specimens. The data recorded in the
five tests
from of the
thetests
five same binder system
measurements film were collected. The mean value of the indexes obtained
five of the same binderwas set as
system filmthe final
were test result.
collected. The mean value of the indexes obtained from
fromthethefive
five measurements
measurements waswas setthe
set as asfinal
the test
finalresult.
test result.

Figure 3. The dumbbell-shaped specimens.

Thedumbbell-shaped
Figure3.3.The
Figure dumbbell-shaped specimens.
specimens.
According to the Chinese standard: GB/T 529-2008 [25], Rubber, vulcanized or thermoplastic,
According to the Chinese standard: GB/T 529-2008 [25], Rubber, vulcanized or thermoplastic,
According tear
we determined to the ChineseTearing
strength. standard: GB/T 529-2008 [25], specimens
Rubber, vulcanized 4)or thermoplastic,
we determined tear strength. Tearingproperties
properties ofof L-shaped
L-shaped (Figure
specimens (Figure were
4) were alsoalso tested
tested
we determined
with an EMT-C
with an EMT-Ctearuniversal
strength.
universal Tearing
material testing
material properties
testing machineofat
machine atL-shaped specimens
roomtemperature
room temperature (Figure
(25(25 °C).
◦ C). 4)
TheThe were
gauge
gauge also tested
length
length of of
with an EMT-C
the specimens
the specimensuniversal
waswasfixed material
at at
fixed 2525mm, testing
mm,and andthe machine
thetensile at room
speedwas
tensile speed temperature
was5050mm/min.
mm/min. (25 °C).
Each
Each The
group
group gauge length
of binder
of the the binderof
the specimens
system films
system was
was
films was fixed
tested atfor
for
tested 25at
at mm,
least5and
least 5timestheto
times tensile
to assessspeed
assess was 50 mm/min.
theexperiment’s
the experiment’s Each group of the binder
reproducibility.
reproducibility.
system films was tested for at least 5 times to assess the experiment’s reproducibility.

Figure L-shaped specimens.

Figure4.4.L-shaped specimens.
Figure 4. L-shaped specimens.
2.6. Viscosity Monitoring Experiment
An SNB-1A digital viscometer was used to monitor the EHTPB-IPDI binder system’s viscosity
changes in the presence of DBTDL and TECH catalysts during the curing process. The binder system
was stirred by a 29# size rotor, with a rotating speed of 0.5 rpm at 25 ◦ C.
 An SNB-1A digital viscometer was used to monitor the EHTPB-IPDI binder system’s viscosity
changes in the presence of DBTDL and TECH catalysts during the curing process. The binder system
was stirred by a 29# size rotor, with a rotating speed of 0.5 rpm at 25 °C.
Coatings 2020, 10, 1266 5 of 15
3. Results and Discussion

3.1. 3. Results and Discussion

Determination of the Activation Energy of EHTPB-IPDI and HTPB-IBDI Binder Systems
A Determination
3.1. non-isothermal
of theDSC method
Activation with
Energy multiple scanning
of EHTPB-IPDI rates was
and HTPB-IBDI selected
Binder Systems to determine the
curing kinetics of the systems.
A non-isothermal DSC methodFigure 5 shows
with multiplethe non-isothermal
scanning curvestoofdetermine
rates was selected the HTPB-IPDI
the curingsystem
recorded at different heating rates. As the heating rate increased, the exothermic
kinetics of the systems. Figure 5 shows the non-isothermal curves of the HTPB-IPDI system recorded peak temperature
shifted to the right,
at different heatingwhile
rates. the shape
As the of the
heating rateexothermic peak
increased, the gradually
exothermic peak widened. With
temperature the increase
shifted to the of
heating
right,rate,
whilenot
the all
shapetheofreactants have peak
the exothermic a curing reaction,
gradually and With
widened. the crosslinking
the increase ofdegree
heating of curing
rate,
not allwas
reaction the not
reactants
high. have
Thermala curing reaction, andoccurs
decomposition the crosslinking
between thedegree of curing
reactant andreaction wascrosslink,
the cured not
andhigh. Thermal decomposition
the exothermic occurs between
peak of decomposition the reactant
overlaps withand
thethe cured crosslink,
exothermic peakand the curing
of the exothermic
reaction.
peak of decomposition overlaps with the exothermic peak of the curing reaction. Therefore,
Therefore, there will be a baseline shift in the DSC curve. The total heat output increased in the same there will
be a baseline shift in the DSC curve. The total heat output increased in the same manner, while the
manner, while the corresponding curing time decreased with the heating rate increase. These
corresponding curing time decreased with the heating rate increase. These changes indicate that
changes indicate that the curing reaction of the HTPB-IPDI system was not only thermodynamically
the curing reaction of the HTPB-IPDI system was not only thermodynamically but also a kinetically
but controlled
also a kinetically
process.
controlled process.

Figure
Figure 5. Non-isothermaldifferential
5. Non-isothermal differential scanning
scanning calorimetry
calorimetry(DSC) curves
(DSC) of the
curves HTPB-IPDI
of the system
HTPB-IPDI at
system at
different heating rates.
different heating rates.
Figure 6 shows the non-isothermal curves of HTPB-IPDI and EHTPB-IPDI systems at a heating
Figure
rate of 5 6◦ C/min.
shows the non
It can be-isothermal curves6 of
seen from Figure HTPB-IPDI
that and EHTPB-IPDI
the initial temperature systems
and peak at a heating
temperature
rateofofexothermic
5 °C/min. peak
It canofbe seen from Figure 6 that the initial temperature and peak temperature
the curing reaction of the EHTPB-IPDI system were lower than that of the of
exothermic
HTPB-IPDI peak of the curing reaction of the EHTPB-IPDI system were lower than that of the
system.
HTPB-IPDI The system.
corresponding peak temperatures, Tp , of the binder systems at different heating rates, listed
in Table 1, were linearly fitted. ln(β/TP2 ) vs. 1/Tp (Figure 7) was plotted according to the Kissinger
method Equation (2), and the pre-exponential factor, A, and activation energy, E, were calculated from
the slope and intercept of the fitting linear curves. The values of the determined pre-exponential factor,
A, and activation energy, E, of the two binder systems are listed in Table 2.
Coatings 2020, 10, 1266 6 of 15
Coatings 2020, 10, x FOR PEER REVIEW 6 of 17

Figure 6.
Figure Non-isothermal DSC
6. Non-isothermal DSC curves
curves of
of the
the HTPB-IPDI
HTPB-IPDI system
system and
and HTPB-IPDI
HTPB-IPDI system
system aa scanning
scanning
rate of 5 ◦ C min−1 .
rate of 5 °C min−1.
Table 1. Data of the EHTPB-IPDI and HTPB-IPDI systems.
The corresponding peak temperatures, Tp, of the binder systems at different heating rates, listed
◦ C·min−1 T 1i /◦ C T 2T 1p /◦ C 1f / C
◦ T 2i /◦ C T 2p /◦ C T 2f /◦ C
in Table 1, were β/
linearly fitted. ln(β/ p ) vs. 1/TpT(Figure 7) was plotted according to the Kissinger
5 167.4 190.4 212.7 174.5 200.1 223.3
method Equation (2),10and the 174.8
pre-exponential
207.8
factor,
239.6
A, and activation
189.5 221.1
energy, E, were calculated
247.4
from the slope and15 intercept of the222.4
181.4 fitting 255.6
linear curves.
196.4 The values263.1
232.7 of the determined
pre-exponential factor,
20 A, and activation
189.1 energy, E,
234.2 of the two
270.2 binder241.9
197.7 systems are
277.4listed in Table 2.
β: heating rate; Ti : initial temperature; Tp : peak temperature; Tf : final temperature; T1 and T2 : curing reaction
temperatures of the EHTPB-IPDI and HTPB-IPDI
Table 1. Data systems. and HTPB-IPDI systems.
of the EHTPB-IPDI

β/°C·min
Table 2. Kinetic T1ithe
−1
parameters of /°Ccuring
T1p/°C T1f/°C
reactions of theTEHTPB-IPDI
2i/°C T2p/°Cand THTPB-IPDI
2f/°C
systems.
5 167.4 190.4 212.7 174.5 200.1 223.3
−1 −1
10 System
174.8 207.8E/kJ·mol
239.6 189.5 A/s 221.1 247.4
15 181.4
EHTPB-IPDI 222.4 53.8
255.6 × 105
196.4 1.79232.7 263.1
Coatings 2020, 10, x FOR PEER20 HTPB-IPDI
REVIEW 189.1 234.2 59.1
270.2 5.29
197.7 241.9× 105 277.4 7 of 17
β: heating rate; Ti: initial temperature; Tp: peak temperature; Tf: final temperature; T1 and T2: curing
reaction temperatures of the EHTPB-IPDI and HTPB-IPDI systems.

Table 2. Kinetic parameters of the curing reactions of the EHTPB-IPDI and HTPB-IPDI systems.

System E/kJ·mol− 1 A/s  −1

EHTPB-IPDI 53.8 1.79 × 105
HTPB-IPDI 59.1 5.29 × 105

Figure 7.7. Determination

Figure Determinationofofactivation
activationenergy,
energy,E, E,
of of
thethe
EHTPB-IPDI andand
EHTPB-IPDI HTPB-IPDI systems,
HTPB-IPDI using
systems, the
using
Kissinger method.
the Kissinger method.

The activation energy of the EHTPB-IPDI binder system was lower than that of the HTPB-IPDI
binder system, indicating the curing reaction of the EHTPB-IPDI binder system was more likely to
occur.

3.2. Analysis of the Glass Transition Temperature, Tg

Coatings 2020, 10, 1266 7 of 15

The activation energy of the EHTPB-IPDI binder system was lower than that of the HTPB-IPDI
binder system, indicating the curing reaction of the EHTPB-IPDI binder system was more likely
to occur.

3.2. Analysis of the Glass Transition Temperature, Tg

The glass transition temperature (Tg ) of polyurethane elastomer reflects its thermal stability and
thermal degradation properties. The Tg value is related to the cross-linking density and chemical structure
of the polyurethane elastomer. Figure 8 indicates that due to epoxy groups’ introduction, Tg of the
EHTPB-IPDI polyurethane elastomer increased by 5 ◦ C, and the thermal stability also improved to a
certain extent. These effects originated from the reaction of the introduced epoxy groups that react with
isocyanate and generate oxazolidinone (Figure 9) during the polyurethane elastomers’ curing process.
There are three positions of C=C in the molecular structure of HTPB (Figure 1). In the epoxidation
reaction, the double bond may be opened to form an epoxy group. With the curing reaction going on,
a large number of oxazolidinones can be produced by the reaction of epoxy group and isocyanate radical.
The existence of oxazolidinone in the binder system may improve the performance of polyurethane
elastomers [26]. The presence of oxazolidinone in polyurethane can increase the glass transition temperature
of polyurethane, which is consistent with the experimental results of Yu et al. [27], polyurethane material
was prepared by the reaction of diglycidyl terephthalate and toluene diisocyanate. The glass transition
temperature was 110 ◦ C, and it had good thermal stability. Besides, the reaction between isocyanate and
epoxy
Coatingsgroups
2020, 10,will branch
x FOR PEER the EHTPB-IPDI binder system and increase its cross-linking density, improving
REVIEW 8 of 17
Coatings 2020, 10, x FOR PEER REVIEW 8 of 17
the elastomer’s thermal stability.

Figure 8. Glass transition temperature (Tg) determined by the DSC thermograms at a scanning rate of
Figure8.8.Glass
Figure Glasstransition
transitiontemperature
temperature(T
(Tgg))determined
determinedbybythe
theDSC
DSCthermograms
thermogramsatataascanning
scanningrate
rateof
of
10◦°C min−1−1 for the EHTPB-IPDI and HTPB-IPDI systems.
10 C min for the EHTPB-IPDI and HTPB-IPDI
10 °C min for the EHTPB-IPDI and HTPB-IPDI systems.
−1 systems.

Figure 9. The reaction

Figure 9. reaction between
between –NCO
–NCO and
and epoxy
epoxy groups.
groups.
Figure 9. The reaction between –NCO and epoxy groups.
3.3. Determination of Mechanical Properties
3.3. Determination of Mechanical Properties
Table 3 shows that the tensile strength of the EHTPB-IPDI polyurethane elastomer was 12%
Table 3 shows that the tensile strength of the EHTPB-IPDI polyurethane elastomer was 12%
higher than that of the HTPB-IPDI elastomer. Besides, compared with EHTPB-IPDI, the tear strength
higher than that of the HTPB-IPDI elastomer. Besides, compared with EHTPB-IPDI, the tear strength
of HTPB-IPDI increased by 17%, while its elongation at break was reduced by 10%. These changes
of HTPB-IPDI increased by 17%, while its elongation at break was reduced by 10%. These changes
can be attributed to the fact that besides the carbamate formation (Figure 10) via the reaction with
Coatings 2020, 10, 1266 8 of 15

3.3. Determination of Mechanical Properties

Table 3 shows that the tensile strength of the EHTPB-IPDI polyurethane elastomer was 12%
higher than that of the HTPB-IPDI elastomer. Besides, compared with EHTPB-IPDI, the tear strength
of HTPB-IPDI increased by 17%, while its elongation at break was reduced by 10%. These changes
can be attributed to the fact that besides the carbamate formation (Figure 10) via the reaction with
hydroxyl groups, isocyanate in the EHTPB-IPDI elastomer can also react with epoxy groups and form
oxazolidinone (Figure 9). Oxazolidinone can improve the mechanical properties of polyurethane [28].
As a result, more branched chains (Figure 11) were generated in the elastomer, yielding the increased
cross-linking density of the polyurethane elastomer and enhancing its tensile and tearing strength,
which is consistent with the experimental results of Yang et al. [29], EHTPB-modified epoxy resin
exhibited excellent mechanical properties than that of neat epoxy resin. Moreover, the increase of the
cross-linking density may block the sliding and movement of the molecular segments, resulting in a
lower fracture growth rate, which is consistent with results from a study by Shen et al. [30].

Table 3. Mechanical properties of the EHTPB-IPDI and HTPB-IPDI systems.

System Tensile Strength (mPa) Elongations at Break (%) Tear Strength (N/mm)
HTPB-IPDI 1.25 ± 0.05 473 ± 23 2.78 ± 0.07
EHTPB-IPDI 1.40
Coatings 2020, 10, x FOR PEER ± 0.03
REVIEW 429 ± 18 3.27 ± 0.05
Coatings 2020, 10, x FOR PEER REVIEW 9 of 17 9 of 17

Figure Figure
10. The10. The reaction
reaction betweenbetween –NCO
–NCO and and –OH.
–OH.

11. The curing

Figure Figure reaction of EHTPB-IPDI binder binder
system forms aforms
network structure.
Figure 11. The11. The curing
curing reactionreaction of EHTPB-IPDI
of EHTPB-IPDI binder systemsystem a network
forms a network structure.
structure.
Compared with the
Compared HTPB-IPDI
with binder system,
the HTPB-IPDI the EHTPB-IPDI binder system Ea and
had lower had
Compared with the HTPB-IPDI binderbinder system,
system, the EHTPB-IPDI
the EHTPB-IPDI binderbinder
systemsystem
had lower lower
Ea Ea
better and
thermal stability and mechanical properties. Therefore, the EHTPB-IPDI binder system was
and better better
thermalthermal stability
stability and mechanical
and mechanical properties.
properties. Therefore,
Therefore, the EHTPB-IPDI
the EHTPB-IPDI binderbinder
systemsystem
selected forselected
was further for
research
furtherin research
this paper.
in this paper.
was selected for further research in this paper.

3.4. Calculation
3.4. Calculation of the Average
of the Average Activation
Activation EnergyEnergy of the EHTPB-IPDI-DBTDL
of the EHTPB-IPDI-DBTDL and EHTPB-IPDI-TECH
and EHTPB-IPDI-TECH
Binder Binder
Systems Systems

3.4.1. Kissinger
3.4.1. Kissinger MethodMethod
The temperature,
The peak peak temperature,
Tp, of Tthe
p, of the EHTPB-IPDI-DBTDL and EHTPB-IPDI-TECH systems at
EHTPB-IPDI-DBTDL and EHTPB-IPDI-TECH systems at
2
Coatings 2020, 10, 1266 9 of 15

3.4. Calculation of the Average Activation Energy of the EHTPB-IPDI-DBTDL and EHTPB-IPDI-TECH
Binder Systems

3.4.1. Kissinger Method

The peak temperature, Tp , of the EHTPB-IPDI-DBTDL and EHTPB-IPDI-TECH systems at different
heating rates (Table 4) was plotted as ln (β/TP2 ) vs. 1/Tp according to the Kissinger method (as shown in
Coatings12)
Figure 2020,
and10, linearly
x FOR PEER REVIEW
fitted. 10 of 17

Figure12.
Figure 12.Fitting
Fitting of the
of the EHTPB-IPDI-DBTDL
EHTPB-IPDI-DBTDL and EHTPB-IPDI-TECH
and EHTPB-IPDI-TECH systemssystems by the equation.
by the Kissinger Kissinger
equation.
Table 4. DSC data of the TECH-catalyzed and DBTDL-catalyzed EHTPB-IPDI curing reaction.
Table 4. DSC
β/data of the
◦ C·min −1 TECH-catalyzed
T /◦ C T and
/◦ C DBTDL-catalyzed
T /◦ C EHTPB-IPDI
T /◦ C T /◦ C curing
T /◦reaction.
C
1i 1p 1f 2i 2p 2f

5 159.5 199.5 216.9 164.2 178.2 199.0

β/°C·min
10
−1 T1i/°C 220.9
169.1
T1p/°C T241.7
1f/°C T2i174.7
/°C T2p/°C204.9
T2f/°C
233.8
15 5 159.5 242.0
180.9 199.5 216.9
265.8 164.2
181.1 178.2220.7 199.0251.8
20 10 182.7
169.1 250.8 279.0
220.9 241.7 187.1 204.9
174.7 232.8 233.8264.4
β: heating rate; Ti : initial15 180.9
temperature; 242.0
TP : peak 265.8Tf : final
temperature; 181.1 220.7 T1251.8
temperature; and T2 : curing reaction
temperatures of the TECH-catalyzed and DBTDL-catalyzed EHTPB-IPDI curing reaction.
20 182.7 250.8 279.0 187.1 232.8 264.4
β: heating
As Figure rate; Ti: initial
12 shows, thetemperature; TP: peakcoefficients,
linear correlation temperature;RT2f: and
finalRtemperature;
2 , of the twoT1 fitting
and T2: lines
curingwere
1 2
reaction temperatures of the TECH-catalyzed and DBTDL-catalyzed EHTPB-IPDI curing reaction.
0.9808 and 0.9994, respectively, indicating a good correlation of the linear fitting curves. The activation
energies of the two systems, E1 and E2 , were 45.4 and 40.3 kJ/mol, 2
respectively.
2
The pre-exponential
As Figure 12 shows, the linear correlation coefficients,
5 R 3 and
−1
factors of two systems, A1 and A2 , were 1.32 × 10 and 5.42 × 101 s , respectively. R2 , of the two fitting lines
were 0.9808 and 0.9994, respectively, indicating a good correlation of the linear fitting curves. The
3.4.2. F-W-Oenergies
activation Method of the two systems, E1 and E2, were 45.4 and 40.3 kJ/mol, respectively. The
pre-exponential factors of two
The peak temperature, systems,
Tp , of A1 and A2, were 1.32
the EHTPB-IPDI-DBTDL and× EHTPB-IPDI-TECH
105 and 5.42 × 103 s−1,systems
respectively.
obtained
at different heating rates (Table 4) was plotted as lnβ vs. 1/Tp (Figure 12) then linearly fitted.
3.4.2.AsF-W-O
FigureMethod
13 shows, the linear correlation coefficients of the two fitting lines, R21 and R22 , were 0.9865 and
0.9995,The
respectively, indicating a good
peak temperature, correlation
Tp, of of the two linear fitting
the EHTPB-IPDI-DBTDL curves.
and From the F-W-O equation,
EHTPB-IPDI-TECH systems
Equation
obtained (3), the activation
at different heating energy of the 4)
rates (Table systems can beascalculated
was plotted lnβ vs. 1/Tfrom the slope
p (Figure 12) thenand intercept
linearly of
fitted.
the fitting line. The determined activation energies of the two systems,
As Figure 13 shows, the linear correlation coefficients of the two fitting E 1 and E ,
lines,
2 R1 and R22 ,
were2 51.0 and

45.8 kJ/mol, respectively.

were 0.9865 and 0.9995, respectively, indicating a good correlation of the two linear fitting curves.
From the F-W-O equation, Equation (3), the activation energy of the systems can be calculated from
the slope and intercept of the fitting line. The determined activation energies of the two systems, E1
and E2, were 51.0 and 45.8 kJ/mol, respectively.
Coatings 2020, 10, 1266 10 of 15
Coatings 2020, 10, x FOR PEER REVIEW 11 of 17

Figure 13. Linear

Figure 13. Linear fitting
fittingof
oflnβ
lnβ vs.
vs. 1/T
1/Tpp for the EHTPB-IPDI-DBTDL
EHTPB-IPDI-DBTDL and
and EHTPB-IPDI-TECH
EHTPB-IPDI-TECH systems
systems
by
by the
the Flynn–Wall–Ozawa
Flynn–Wall–Ozawa(F-W-O)(F-W-O)equation.
equation.

The
Theactivation
activationenergy
energyobtained
obtained bybythethe
FWO FWO method was was
method slightly higher
slightly than that
higher thancalculated using
that calculated
the Kissinger method, the reason for the slightly higher activation energy is
using the Kissinger method, the reason for the slightly higher activation energy is that there is athat there is a certain
difference in the formula
certain difference fitting between
in the formula the FWOthe
fitting between method
FWOand the Kissinger
method method, but
and the Kissinger this does
method, not
but this
affect the affect
does not accuracy of the result,
the accuracy which
of the result,is consistent with results
which is consistent withfrom other
results fromstudies,
other e.g., the e.g.,
studies, studies
the
by Lee et al. [31] and Liu et al. [32]. The difference in the activation energy could
studies by Lee et al. [31] and Liu et al. [32]. The difference in the activation energy could originateoriginate from the
limitations of the used
from the limitations of equations. Still, it is Still,
the used equations. not related
it is nottorelated
the characteristics of the studied
to the characteristics of thesystems.
studied
Therefore, the kinetics of the curing reaction of the EHTPB-IPDI-TECH
systems. Therefore, the kinetics of the curing reaction of the EHTPB-IPDI-TECH and and EHTPB-IPDI-DBTDL
binder systems can be binder
EHTPB-IPDI-DBTDL fitted with the nth-order
systems can be fittedreaction
with model.
the nth-order reaction model.
3.4.3. Doyle Method
3.4.3. Doyle Method
The DSC data listed in Table 3 were analyzed using the Doyle method. lnβ vs. 1/Tp was plotted
The DSC data listed in Table 3 were analyzed using the Doyle method. lnβ vs. 1/Tp was 2
plotted
2
(Figure 13) and linearly fitted. The linear correlation coefficients of the two fitted lines, R 2 1 and R22,
(Figure 13) and linearly fitted. The linear correlation coefficients of the two fitted lines, R1 and R2
were 0.9808 and 0.9994, respectively, which indicates a good linear correlation. The activation energies E1
, were
and E2 of0.9808 and
the two 0.9994,calculated
systems, respectively,
from which indicates
the fitted a good
lines’ slopes, linear
were correlation.
44.9 and Therespectively.
40.8 kJ/mol, activation
energies E1 and E2 of the two systems, calculated from the fitted lines’ slopes, were 44.9 and 40.8 kJ/mol,
3.4.4. Average Activation Energy
respectively.
Table 5 shows the average activation energy calculated using the Kissinger, F-W-O and Doyle methods.
3.4.4. Average Activation Energy
The average activation energy values, ∆E1 and ∆E2 , of the two systems were 47.1 and 42.3 kJ/mol,
Table 5The
respectively. shows theshow
results average activation
that the averageenergy calculated
activation energy ofusing the Kissinger, F-W-O
the EHTPB-IPDI-DBTDL andsystem
binder Doyle
methods.
was lower, The
and average
the initialactivation energy values,
reaction temperature was ΔE 1 and
lower andΔE 2 , of
the the two
reaction systems
activity waswere 47.1
higher. It and
has
42.3 kJ/mol,
reference respectively.
value for the design ofThecuringresults
formulashow
at roomthat the average activation energy of the
temperature.
EHTPB-IPDI-DBTDL binder system was lower, and the initial reaction temperature was lower and
Tableactivity
the reaction R2 ofhigher.
5. Ea andwas the curing reaction
It has calculated
reference valueby Kissinger, F-W-O of
for the design andcuring
Crane equation.
formula at room
temperature. 2
Binder System Ea (kJ/mol) Correlation Coefficient R

Table 5. -Ea and R2 of the curing

Kissinger
reaction F-W-O
calculated Doyle Kissinger
by Kissinger, F-W-Oequation.
F-W-O and Crane Doyle
HTPB-IPDI-TECH 45.4 51.0 44.9 0.9808 0.9865 0.9865
Binder System
EHTPB-IPDI-DBTDL 40.3 Ea (kJ/mol)
45.8 40.8 Correlation
0.9994 Coefficient
0.9995 R2
0.9995
F-W-
- Kissinger Doyle Kissinger F-W-O Doyle
O
HTPB-IPDI-TECH 45.4 51.0 44.9 0.9808 0.9865 0.9865
EHTPB-IPDI-DBTDL 40.3 45.8 40.8 0.9994 0.9995 0.9995
 Coatings 2020, 10, x FOR PEER REVIEW 12 of 17
Coatings 2020, 10, 1266 11 of 15

3.5. Monitoring of Viscosity

3.5. Monitoring of Viscosity
The viscosity, or precisely the viscosity growth rate of the EHTPB binder system, increases with
the progress of the curing reaction. It grows rapidly around the gelation point of the system and
The viscosity, or precisely the viscosity growth rate of the EHTPB binder system, increases with
approaches infinity when the system is completely cured. In this research, it is not completely cured,
the progress of the curing reaction. It grows rapidly around the gelation point of the system and
which is the early stage of curing reaction. The temperature of exothermic peak of curing reaction
approaches infinity when the system is completely cured. In this research, it is not completely cured,
can be obtained from the DSC curve, full chemical curing can not be seen from finalization of the
which is the early stage of curing reaction. The temperature of exothermic peak of curing reaction can
DSC peak. It can be seen from the FTIR spectrum, the disappearance of reaction groups and the
be obtained from the DSC curve, full chemical curing can not be seen from finalization of the DSC
formation of new groups.
peak. It can be seen from the FTIR spectrum, the disappearance of reaction groups and the formation
Figure 14 shows the viscosity increase of the EHTPB-IPDI binder system in the presence of two
of new groups.
catalysts, DBTDL and TECH, at the curing temperature of 25 °C. The pot life of the binder system for
Figure 14 shows the viscosity increase of the EHTPB-IPDI binder system in the presence of two
solid rocket propellants and PBXs is usually defined as ◦the consumed time when the system
catalysts, DBTDL and TECH, at the curing temperature of 25 C. The pot life of the binder system for
viscosity increases to 20,000–25,000 mPa·s [33,34]. From the results of viscosity build-up
solid rocket propellants and PBXs is usually defined as the consumed time when the system viscosity
measurement under the same curing temperature, it is possible to conclude that the pot-life of
increases to 20,000–25,000 mPa·s [33,34]. From the results of viscosity build-up measurement under
EHTPB-IPDI-TECH system was longer than that of EHTPB-IPDI-DBTDL system. The viscosity
the same curing temperature, it is possible to conclude that the pot-life of EHTPB-IPDI-TECH system
growth rate (first derivation of the viscosity curve in Figure 14) of the EHTPB-IPDI binder system
was longer than that of EHTPB-IPDI-DBTDL system. The viscosity growth rate (first derivation of the
was higher for DBTDL than for TECH, indicating a higher catalytic activity of DBTDL, which is
viscosity curve in Figure 14) of the EHTPB-IPDI binder system was higher for DBTDL than for TECH,
consistent with the results obtained from DSC tests. EHTPB-IPDI-DBTDL binder system had higher
indicating a higher catalytic activity of DBTDL, which is consistent with the results obtained from DSC
reaction activity and faster viscosity growth. For the curing reaction of EHTPB-IPDI binder system,
tests. EHTPB-IPDI-DBTDL binder system had higher reaction activity and faster viscosity growth. For
the catalytic effect of DBTDL was better than that of TECH, which is consistent with the
the curing reaction of EHTPB-IPDI binder system, the catalytic effect of DBTDL was better than that of
experimental results of Ma et al. [15].
TECH, which is consistent with the experimental results of Ma et al. [15].

Figure 14.Change
Figure14. Changeof
ofviscosity
viscosityof
ofthe
theEHTPB-IPDI
EHTPB-IPDIbinder
bindersystem
systematatthe
thecuring
curingtemperature 25◦ °C.
temperatureofof25 C.

3.6.
3.6.Curing
CuringReaction
ReactionKinetic
KineticEquations
EquationsofofthetheEHTPB-IPDI-DBTDL
EHTPB-IPDI-DBTDL andand
EHTPB-IPDI-TECH
EHTPB-IPDI-TECH Binder Systems
Binder
After determining the ∆E of the systems, the curing reaction’s order can be obtained using the Crane
Systems
equation
After(Equation (5)). lnβ
determining thevs.
ΔE1/T wassystems,
of pthe plotted and linearlyreaction’s
the curing fitted. Theorder
equations
can beof obtained
the two fitted
usinglines
the
obtained using the F-W-O method, y1 = −6.457x + 15.303 and y2 = −5.797x + 14.447,
Crane equation (Equation (5)). lnβ vs. 1/Tp was plotted and linearly fitted. The equations of the two were substituted
into Equation
fitted (5). The using
lines obtained curingthe
reaction
F-W-Oorders
method,of the
y1 two systems
= −6.457x (n1 and
+ 15.303 n2 )y2
and were calculated
= −5.797x to be were
+ 14.447, 0.95
and 0.95, respectively. Since the reaction orders for the two systems are both non-integers,
substituted into Equation (5). The curing reaction orders of the two systems (n1 and n2) were the reaction
rate of curing
calculated to reaction is not
be 0.95 and onlyrespectively.
0.95, related to the concentration
Since of reactants,
the reaction orders forbut
thealso
twodepends
systems onareother
both
non-integers, the reaction rate of curing reaction is not only related to the concentration of reactants,
but also depends on other factors, so it is a complex reaction. The equations of the curing reaction
kinetics of the binder systems can be expressed as follows:
Coatings 2020, 10, 1266 12 of 15

factors, so it is a complex reaction. The equations of the curing reaction kinetics of the binder systems
can be expressed as follows:

d∂ 3
EHTPB-IPDI-DBTDL : = 1.32 × 105 e−5.7×10 /T (1 − ∂)0.95 (6)
dt
Coatings 2020, 10, x FOR PEER REVIEW 13 of 17
d∂ 3
EHTPB-IPDI-TECH : = 5.42 × 103 e−5.1×10 /T (1 − ∂)0.95 (7)
dt
EHTPB-IPDI-DBTDL： = 1.32 × 10 e . × / (1 − 𝜕) . (6)
3.7. Parameters Optimization in the Curing Process
DSC curves show that when the system was cured by a dynamic heating method, the curing
. × /
temperature variedEHTPB-IPDI-TECH
with the heating rate. = 5.42 × 10
： Besides, (1 − ∂) . also changed, so (7)
the epeak temperature the
determination of the actual curing temperature was challenging. To obtain a reliable curing temperature,
the characteristic curing temperature at a zero heating rate was obtained by the extrapolation method.
3.7. Parameters Optimization in the Curing Process
Specifically, the initial (Ti ), peak (Tp ) and final (Tf ) temperatures of the curing process at the-zero heating
were DSC curves
obtained byshow that when
extrapolating thethe systemrate
heating wastocured by a dynamic
zero (Table heatinginmethod,
6). As shown Figures the curing
15 and 16,
temperature
when varied
the heating ratewith
of thetheEHTPB-IPDI-TECH
heating rate. Besides, thesystem
binder peak temperature
was extrapolated also to changed,
zero, Ti so the
of the
determination
curing process wasof the ◦ C, T curing
153actual temperature was 185 ◦ C and To
challenging. Tf ofobtain a reliable curing
p of the exothermic peak was the curing process was
198 ◦
temperature, characteristic
C; when the heating rate ofcuring temperature at a zero
the EHTPB-IPDI-DBTDL binder heating
systemrate waswas obtained to
extrapolated byzero,
the
Textrapolation
of the curing method.
process was 158 ◦ C, Ttheofinitial
Specifically, the (T ), peak
exothermic
i (T
peak
p ) and
wasfinal
164 ◦ Cf)and
(T temperatures
T of the of
curingthe curing
process
i p f
184 ◦atC.the-zero heating were obtained by extrapolating the heating rate to zero (Table 6). As
process
was
shown in Figures 15 and 16, when the heating rate of the EHTPB-IPDI-TECH binder system was
6. Initial,
Table to
extrapolated zero, TPeak and Final temperatures of EHTPB-IPDI-TECH and EHTPB-IPDI-DBTDL.
i of the curing process was 153 °C, Tp of the exothermic peak was 185 °C and Tf

of the curing
Systemprocess was 198 °C;
Initial when the(◦ heating
Temperature C) rate
Peak of the EHTPB-IPDI-DBTDL
Temperature (◦ C) binder (system
Final Temperature ◦ C)
was extrapolated to zero, Ti of the curing process was 158 °C, Tp of the exothermic peak was 164 °C
EHTPB-IPDI-TECH 153 185 198
andEHTPB-IPDI-DBTDL
Tf of the curing process was 184 158°C. 164 184

Figure 15. Extrapolation diagram of the curing reaction temperature at a zero heating rate for the
Figure 15. Extrapolation diagram of the curing reaction temperature at a zero heating rate for the
EHTPB-IPDI-TECH system.
EHTPB-IPDI-TECH system.
Coatings 2020, 10, 1266 13 of 15
Coatings 2020, 10, x FOR PEER REVIEW 14 of 17

Figure 16. Extrapolation

Figure16. Extrapolation diagram
diagram of
of the
the curing
curing reaction
reaction temperature
temperature at
at aa zero
zeroheating
heating rate
ratefor
forthe
the
EHTPB-IPDI-DBTDL system.
EHTPB-IPDI-DBTDL system.

The curing
Table timePeak
6. Initial, can be
andexpressed by the curing
Final temperatures degree (∂) relativeand
of EHTPB-IPDI-TECH to the curing speed. According to
EHTPB-IPDI-DBTDL.
the calculation results, assuming ∂ was 99%, the curing times of the two systems were 4 and 19 h. The curing
System
temperature and the curing Initial
time Temperature (°C) Peakwere
of EHTPB-IPDI-DBTDL Temperature
lower than(°C) Final
those Temperature (°C)
of EHTPB-IPDI-TECH.
TheEHTPB-IPDI-TECH
cured thermosetting materials of153 the EHTPB-IPDI-DBTDL 185 and EHTPB-IPDI-TECH binder 198 systems
EHTPB-IPDI-DBTDL 158
were obtained under the curing conditions listed in Table 7. 164 184

The curing
Table timeexpressions
7. Analytical can be expressed by and
for curing rate the curing
curing degree
time, (∂)
and the relative
values of the to the time
curing curing
of thespeed.
According to the calculation
EHTPB-IPDI-DBTDL ∂ was 99%, the curing times of the two systems were
results, assumingsystems.
and EHTPB-IPDI-TECH
4 and 19 h. The curing temperature and the curing time of EHTPB-IPDI-DBTDL were lower than
System
those of EHTPB-IPDI-TECH. TheCuring
curedRate (d∂/dt)
thermosettingCuring Timeof
materials (t) the Curing Time (h)
EHTPB-IPDI-DBTDL and
EHTPB-IPDI-TECH binder systems were obtained under the ∂
curing conditions listed in Table 7.
0.95 t= d∂/dt
EHTPB-IPDI-DBTDL 0.31(1 − ∂) ∂
4
= 0.95
0.31(1−∂)
Table 7. Analytical expressions for curing rate and curing time, and
∂ the values of the curing time of
0.95 t = d∂/dt
the EHTPB-IPDI-DBTDL
EHTPB-IPDI-TECH 0.08(1 − ∂)
and EHTPB-IPDI-TECH systems. ∂
19
= 0.95
0.08(1−∂)
System Curing Rate (𝐝𝛛⁄𝐝𝒕) Curing Time (t) Curing Time (h)
∂
4. Conclusions 𝑡=
d ∂ ⁄dt
EHTPB-IPDI-DBTDL 0.31(1 − 𝜕) . ∂ 4
In this paper, the curing kinetics of EHTPB-IPDI and HTPB-IPDI
= binders were studied by the DSC
method, and the related mechanical properties were measured. 0.31(1 − ∂) .temperature, Ti , and activation
The initial
∂
𝑡 = of the HTPB-IPDI system. Compared
energy, Ea , of the EHTPB-IPDI curing reaction were lower than those
d ∂⁄dt
with the HTPB-IPDI binder system, 0.08(1
EHTPB-IPDI-TECH the Tg − the. EHTPB-IPDI binder system was increased
of 𝜕) 19 by 5 ◦ C,
∂
indicating better thermal stability of the EHTPB-IPDI binder = system. The. tensile strength and breaking
0.08(1 − ∂)
strength of the EHTPB-IPDI system were increased by 12% and 17%. In comparison, its elongation at break
was decreased by 10%, indicating better mechanical properties of the EHTPB-IPDI binder system. When
4. Conclusions
DBTDL and TECH were used as catalysts in the EHTPB-IPDI system, the Ea of the EHTPB-IPDI-DBTDL
binderInsystem
this paper,
was the curing
lower than kinetics of EHTPB-IPDI
that of the EHTPB-IPDI-TECHand HTPB-IPDI binders
binder system. were
This studiedthat
indicates by thethe
DSC method, and the related mechanical properties were measured. The initial temperature,
EHTPB-IPDI-DBTDL system had a higher reactivity, and its curing process occurred at lower temperatures. T i, and

activation
In summary,energy, Ea, of thebinder
the EHTPB-IPDI EHTPB-IPDI curing
system had reaction
a lower were
reaction lower than
initiation those ofhigher
temperature, the HTPB-IPDI
reactivity
system. Compared with the HTPB-IPDI binder system, the T g of the EHTPB-IPDI binder system was
and was more prone to curing reaction at room temperature. This is of reference value for the design of
increased by 5 °C, indicating better thermal stability of the EHTPB-IPDI binder system. The tensile
the room temperature curing formula of polyurethane materials. Due to the introduction of epoxy groups,
strength and breaking strength of the EHTPB-IPDI system were increased by 12% and 17%. In
the cured film of EHTPB-IPDI had good mechanical properties and thermal stability. It can be used for
comparison, its elongation at break was decreased by 10%, indicating better mechanical properties
of the EHTPB-IPDI binder system. When DBTDL and TECH were used as catalysts in the
EHTPB-IPDI system, the Ea of the EHTPB-IPDI-DBTDL binder system was lower than that of the
EHTPB-IPDI-TECH binder system. This indicates that the EHTPB-IPDI-DBTDL system had a higher
Coatings 2020, 10, 1266 14 of 15

composite solid propellant and solid rocket motor insulation and lining materials, and has a wide range
of application prospects.

Author Contributions: Y.L., Z.M., and T.C. conceived and designed the experiments; X.Z. and K.J. performed the
experiments; X.Z. analyzed the data; X.Z. and K.J. contributed reagents/materials/analysis tools; X.Z. wrote the
paper. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Conflicts of Interest: The authors declare no conflict of interest.

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