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org/IECR Article

Chemical Modification of Hydroxyl-Terminated Polybutadiene and

Its Application in Composite Propellants
Pingan Zhang, Wenjiayi Tan, Xilong Zhang,* Juan Chen, Jianmin Yuan, and Jianru Deng*
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ABSTRACT: In this article, hydroxyl-terminated polybutadiene

(HTPB) was chemically transformed into multiamine, hydroxy
polybutadiene (AEHTPB) by the adoption of appropriate
synthesis strategies. The structure of AEHTPB was confirmed by
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Fourier transform infrared spectroscopy (FT-IR) and nuclear

magnetic resonance (NMR). The modification degree was altered
by adjusting reaction conditions to find out the effect of structural
change on various physical properties, including the viscosity and
glass transition temperature (Tg) of AEHTPB. Adding AEHTPB to
the HTPB binder system could improve the cross-link density and
strength of the polyurethane elastomer. Meanwhile, the experiment
results indicated that AEHTPB could inhibit the low-temperature
decomposition of ammonium perchlorate (AP) by forming a dense
coating on the surface of AP. Then, the propellant level studies were conducted with the use of AEHTPB/HTPB mixture as a
binder. As a result, the burning rate of propellant containing AEHTPB (5 wt %) was found to be reduced by 10.8% compared to
HTPB-based propellant, and the mechanical properties of the propellant were superior to those of HTPB-based propellant with an
improvement of 46.2% in tensile strength and 35.1% enhancement in elongation at break. Finally, tensile testing and observation of
fracture surface morphology further demonstrated that AEHTPB had a significant bonding effect on AP-based propellant.

1. INTRODUCTION substances have poor compatibility with HTPB propellants,

HTPB propellant is a type of composite solid propellant with
hydroxyl-terminated polybutadiene (HTPB) as a polymeric
binder. Because of its technical maturity, low cost, and good
combination property, it is widely applied to various strategic
and tactical solid missiles.1−5 At present, the propellant is
developing toward high thrust and strong antioverload
capability, which requires the solid propellant used to have
both high energy density and good mechanical properties.6,7
Meanwhile, in practice, some new booster rockets and cruise
missile engines also need the propellant to have a lower
burning rate to ensure long-term sustained and stable thrust.8,9
For HTPB propellant, the reduction of the burning rate is
mainly achieved by adding the burning-rate depressant to
inhibit the thermal decomposition of ammonium perchlorate
(AP).10,11 The most commonly used burning-rate depressants
in HTPB propellants are inorganic salts, such as ammonium
oxalate ((NH4)2C2O4),12,13 calcium carbonate (CaCO3),14,15
and strontium carbonate (SrCO3).16,17 However, these
burning-rate depressants do not contribute to the energy of
the propellant, and it is necessary to use these additives in
rather substantial quantities if the desired burning suppression
is to be obtained, which will reduce the energy density and
mechanical properties of the propellant.18,19 Some of the
literature reported that quaternary ammonium salts have a
significant effect of reducing the burning rate,20 but these
and a small amount of addition will cause adverse effects on
the propellants.
On the other hand, with the continuous requirements of
energy in propellants, the content of solid fillers is increasing
higher and higher (up to 90%), which brings an enormous
challenge to the mechanical properties of propellant grains.
However, as a nonpolar binder, HTPB does not has strong
interfacial bonding with polar fillers, and thus undergoes
dewetting (debonding) upon deformation. Dewetting will
adversely affect the mechanical properties, combustion
performance, and storage stability of the propellant.21,22 To
improve the performance of the propellant, it is usually
necessary to add a variety of functional additives to the
propellant formulation, for example, bonding agents,23,24
burning-rate modifiers,25,26 process additives,27 and plasti-
cizers.28 However, this makes the propellant composition more
complicated and it is more difficult to control quality. Also, the
Received: December 16, 2020
Revised: February 22, 2021
Accepted: February 22, 2021
Published: March 4, 2021

© 2021 American Chemical Society https://dx.doi.org/10.1021/acs.iecr.0c06172

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Industrial & Engineering Chemistry Research
effect of these additives will be reduced due to the antagonism
between components and poor thermodynamic compatibility
with the binder matrix.
In this paper, we report a novel approach of functionaliza-
tion of HTPB to multiamine, hydroxy polybutadiene
(AEHTPB) by chemical modification. The hydroxyl group in
the AEHTPB molecule can increase the cross-link density of
the binder matrix through the curing reaction, and the amine
group not only has an interface bonding effect on AP but also
can inhibit its thermal decomposition. Above all, the AEHTPB
has natural miscibility with HTPB. This work has described the
synthesis and characterization of AEHTPB, and we have also
made efforts to research the influence of AEHTPB on the
thermal decomposition of AP as well as the effect on the
mechanical properties of the binder matrix and propellant.
2. EXPERIMENTAL SECTION
2.1. Raw Materials. The HTPB used has a molecular
weight (Mn) of ∼4000 g/mol (composed by 20 mol % 1,2-
addition structure and 80 mol % 1,4-addition structure
microstructures) and a hydroxyl value of 28.5 mg of KOH/g.
It was purchased from Zibo Qilong Chemical Industry Co. Ltd.
(China) and used as received without any further purification.
Isophorone diisocyanate (IPDI), hydrogen peroxide (H2O2),
diethylamine, and acetic acid were procured from Sinopharm
Chemical Reagent Co. Ltd. (China). Ammonium perchlorate
(AP, 100 mesh) and hexogen (RDX, 100 mesh) were kindly
provided by Jianghe State Chemical Plant (China). All the
solvents were dried and distilled before use. All other chemicals
were at the highest purity available and used without further
purification.
2.2. Synthesis. 2.2.1. Synthesis of Epoxidized HTPB. The
epoxidation of HTPB (EHTPB) was carried out by peroxide
acetic acid in situ (Scheme 1).29,30 Briefly, the procedure for
Scheme 1. Synthesis Scheme for EHTPB
the synthesis of EHTPB is as follows: HTPB (30 g) was
dissolved in a mixture of dichloromethane (100 mL) and acetic
acid (24 g) solution and then introduced into the reactor,
which was submerged in a well-controlled-temperature water
bath. Sodium tungstate dihydrate (0.3 g) was completely
dissolved in a 30 wt % hydrogen peroxide aqueous solution (60
g). The solution was put into the reactor while stirring to start
the reaction. The reaction was carried out at 60 °C for 3 h.
After that, the stirring was stopped, and the two phases were
separated. The organic solvents were washed with distilled
water (3 × 100 mL) and allowed to evaporate. Then, the
residue was dried under a vacuum at 60 °C for 12 h. The
product is a colorless viscous liquid with a yield of 98%.
2.2.2. Synthesis of Multiamine, Hydroxy Polybutadiene.
Scheme 2 shows the synthesis scheme for multiamine, hydroxy
polybutadiene (AEHTPB).
2.3. Preparation of Elastomers. The elastomers based on
theHTPB/AEHTPB binder system were prepared with IPDI at
a stoichiometry ratio (NCO/OH) of 1.0 without any catalyst.
First, HTPB and AEHTPB were stirred evenly at 50 °C and
then mixed with a calculated amount of IPDI. Furthermore,
the above mixture was poured into a polytetrafluoroethylene
mold and held under vacuum for 30 min at 40 °C to remove
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Scheme 2. Synthesis Scheme for AEHTPB
bubbles in the mixture. Finally, the mixture was cured at 60 °C
for 7 days. The cured elastomers were cut into appropriate size
specimens for mechanical performance testing.
2.4. Preparation of Composite Propellants. The
prepared AEHTPB was further applied to the HTPB
propellant, and the detailed propellant composition is provided
in Table 1. Figure 1 shows the preparation process of the
Table 1. HTPB Propellant Compositiona
constituent percentage (wt %)
binder system (HTPB/AEHTPB/IPDI) 12
RDX 10
AP 63
Al 15
a
AEHTPB accounts for 5% of the binder system mass. Curing ratio
NCO/OH = 1.0.
Figure 1. Manufacturing process of HTPB propellant.
propellant sample. The AEHTPB was first mixed with HTPB
at 50 °C in the mixer. Then, the mixture was moved to a
vertical kneader; Al powder, RDX, and AP were added
gradually with stirring. Finally, the required amounts of curing
agents were added and mixed thoroughly, followed by
degassing in a vacuum oven at 40 °C and curing at 60 °C
for 7 days. The cured propellant samples were tested for
mechanical properties.
2.5. Characterization Techniques. 2.5.1. Structural
Characterization. Fourier transform infrared (FTIR) spectra
were recorded on a Nicolet IS10 FTIR spectrometer in the
range 500−4000 cm−1, and the polymers were coated on a KBr
disk to form the film. 1H NMR and 13C NMR spectra were
recorded on a Bruker Avance-III 400 (400 MHz) spectrometer
in CDCl3 solvent.
2.5.2. Thermal Study. The thermal behaviors of AEHTPB
and the AEHTPB/HTPB mixture were analyzed with a
differential scanning calorimeter (DSC) technique. DSC was
performed with a TA Instruments Q500 in a nitrogen
atmosphere. About 5 mg of the sample was heat-treated
from −120 °C to room temperature at a heating rate of 10 °C/
min.
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The effect of AEHTPB on the decomposition behavior of
AP was evaluated by thermogravimetry−differential scanning
calorimetry (TG−DSC) analysis. The TG−DSC measure-
ments were carried out with a Netzsch STA449F5 under
nitrogen atmosphere (50 mL/min) at 10 °C/min heating rate,
from room temperature to 600 °C.
2.5.3. Determination of Cross-Link Density. The cross-link
density of the elastomer was measured by the swelling method.
The cured elastomer samples were cut into pieces of
approximately 7 × 7 × 3 mm3 size and soaked in toluene for
72 h. The sample was weighed after the solvent was gently
wiped off. From the swell ratio, the cross-link density was
calculated by using the Flory−Rehner equation.
2.5.4. Mechanical Property. The static mechanical proper-
ties of the cured polymers and propellants were evaluated by
using a universal testing machine (INSTRON Model 5582).
Dumbbell specimens were cut following ASTM D412 and
GJB770B-2005 standard methods, and the tests were
performed at a temperature of 25 °C at a cross-head speed
of 100 mm/min. Three specimens of each elastomer and
propellants at least were tested, and the average values were
reported.
2.5.5. Burning Rate. The burning rates were measured by
the strand burner method (GJB 770B-2005 test method of
propellant) at 20 °C. Each batch of sample was tested under
four different pressure points between 2 and 10 MPa with
three repetitions, and the average values were reported. Then,
the pressure exponents were calculated by Vieille’s law (r =
bpn).
2.5.6. Microscopic Study. The fracture morphologies of
propellant specimens were shown by a scanning electronic
microscope (Hitachi S-4800, Japan) operated at 15 kV.
3. RESULTS AND DISCUSSION
3.1. Polymer Characterization. The FTIR spectra of
HTPB, EHTPB, and AEHTPB are enumerated in Figure 2. In
the FTIR spectrum of HTPB (Figure 2a), the characteristic
peak at 725 cm−1 is related to 1,4-cis double bonds, that at 965
cm−1 is related to 1,4-trans double bonds, and that at 910 cm−1
is related to 1,2-vinyl double bonds.31 For EHTPB (Figure
2b), the absorption peaks of 1,4-cis and 1,4-trans double bonds
Figure 2. FTIR spectra of (a) HTPB, (b) EHTPB, and (c) AEHTPB.
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are reduced, but the position of the 1,2-vinyl double bonds
remained constant, revealing that the epoxidation reaction
mainly occurs on the 1,4-(cis and trans) double bonds. The
adsorption peak at 1240 cm−1 confirms the presence of the
epoxide group (C−O−C, stretching vibration) in EHTPB.32
In the case of AEHTPB (Figure 2c), an obvious peak centered
at 1070 cm−1 corresponds to the secondary alcohol (C−O,
stretching vibration) and disappearance of epoxide group
absorption at 1240 cm−1. Also, the broad signal at 3400−3600
cm−1 and that related to the hydroxyl group (hydrogen bond)
of AEHTPB are enhanced, indicating a complete conversion of
EHTPB to AEHTPB.
Figure 3 displays 13C NMR spectra of (a) HTPB, (b)
HTPB, and (c) AEHTPB. In the 1H NMR spectrum of HTPB,
the peaks at 5.4−5.5 (a) and 4.9 ppm (b) are assigned to 1,4-
(cis and trans) protons and 1,2-vinyl protons, respectively. For
EHTPB (Figure 3b), the absorption at 2.7 ppm (c)
corresponds to the trans epoxy protons, whereas the one at
2.9 ppm (d) corresponds to the cis epoxy protons. According
to the research from Gemmer and Golub,33 the vinyl epoxy
group proton has absorption at 2.5 ppm (e). However, we did
not find a peak at 2.5 ppm, which further verified the
conclusion from the FTIR results that the epoxidation reaction
occurred mainly on the 1,4-(cis and trans) double bonds of
HTPB. From Figure 3c, it is clear that the peaks corresponding
to epoxy protons have disappeared. Moreover, the multiple
peaks at 1.0−1.1 (f) and 2.4−2.7 ppm (g) are attributed to the
methyl protons and methylene protons of diethylamine,
respectively. All the above results suggest that AEHTPB is
successfully prepared. The corresponding assignments of
chemical shifts (δ, ppm) from 1H NMR and 13C NMR of
HTPB, EHTPB, and AEHTPB are presented in the Supporting
Information.
By controlling the epoxidation reaction of HTPB, we
prepared a series of AEHTPBs with modification degrees of
10, 15, 20, and 25% and named them AEHTPB10% ,
AEHTPB15%, AEHTPB20%, and AEHTPB25%, respectively
(the numbers represent the percentage of double bonds
modified in HTPB). The physicochemical properties, such as
density, viscosity, glass transition temperature (Tg), hydroxyl
value, and amine value of the product, were measured. The
results are displayed in Table 2.
Viscosity and glass transition temperature are important
performance indicators of propellant binder, which determine
the processing performance and low-temperature mechanical
properties. As can be seen from Table 2, the modification
degree is critical in determining the properties of the product.
The viscosity and the glass transition temperature of AEHTPB
are both increased with the increasing modification degree.
The reasons are mainly from two aspects: first, the
modification process destroyed the double bond in HTPB
and introduced bulky groups (hydroxyl and tertiary amine
groups) onto the backbone, which reduced the flexibility of the
molecule; second, these polar groups interact with each other,
increasing the interaction between molecules.36 When the
modification degree on the HTPB exceeds 20%, the viscosity
of AEHTPB increases sharply, which will affect its processing
and usage performance. However, the potential to change the
properties is an important point since different users may have
different requirements, such as more or fewer functional
groups, higher or lower viscosity, and higher or lower Tg, all of
which are controllable by variation in the modification
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Figure 3. 13C NMR spectra of (a) HTPB, (b) EHTPB, and (c) AEHTPB.

Table 2. Physicochemical Properties of AEHTPB with Different Degrees of Modification

viscosity (Pa·s)
sample a 3
density (kg/m ) Mn 30 °C 50 °C Tg (°C) hydroxyl valueb (mmol/g) amine valuec (mmol/g)
HTPB 0.887 4255 9.6 5.0 −91.5 0.470 −
AEHTPB10% 0.920 4986 46.3 14.2 −72.7 1.648 1.178
AEHTPB15% 0.925 5260 88.4 23.5 −55.5 2.252 1.785
AEHTPB20% 0.934 5685 275.0 62.4 −45.9 2.721 2.238
AEHTPB25% 0.946 5952 568.1 168.3 −31.7 3.031 2.551
a
Density is measured by specific gravity method at room temperature. bHydroxyl value is determined by acetic anhydride/N-methylimidazole
method.34 cAmine value is determined by nonaqueous titration.35

degree.37 The follow-up research uses AEHTPB15% as the

analysis object.
3.2. Compatibility Analysis. As a propellant binder
system, AEHTPB and HTPB should have good miscibility to
ensure that AEHTPB can evenly disperse in the HTPB matrix.
The miscibility of blends can be characterized using
thermoanalytical techniques, such as differential scanning
calorimetry (DSC).38,39 As a rule, miscible mixtures show a
single Tg between the two components, if the two component
Tg values are more than 20 °C apart. In contrast, the
immiscible mixtures often possess several glass transition
temperatures corresponding to the components of the blend.
In other words, changes in Tg are governed by the miscibility
of two mixing components.40
Physical mixtures of AEHTPB and HTPB were prepared at
three mass ratios (1:9, 2:8, 3:7) by geometric mixing. Figure 4
depicts the DSC thermograms of AEHTPB/HTPB mixtures at Figure 4. DSC thermograms of (a) HTPB, (b) AEHTPB/HTPB
various ratios. As we can see, the glass transition temperatures (1:9), (c) AEHTPB/HTPB (2:8), (d) AEHTPB/HTPB (3:7), and
of HTPB and AEHTPB are detected to be −91.2 and −55.7 (e) AEHTPB.
°C, respectively. In terms of AEHTPB/HTPB mixtures, there
is only one obvious step in each curve, which means the
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Figure 5. Stress−strain curves of elastomers with different mass ratios of AEHTPB: (a) 0−5 and (b) 5−25 wt % AEHTPB content.

AEHTPB/HTPB mixture exhibits a single Tg, and the Tg is calculated by using the data obtained from the swelling
close to that of HTPB. Therefore, the AEHTPB/HTPB experiment based on the Flory−Rehner equation:44,45
systems are completely compatible and have good low-
temperature performance. From the perspective of molecular Me = −Vsρp (Vp1/3 − Vp/2)/[ln(1 − Vp) + Vp + χVp2]
structure, although a large number of tertiary amine groups (1)
and hydroxyl groups are introduced into the AEHTPB where Vs is the molar volume of the solvent, Vp is the volume
molecule, the main chain structure is still similar to that of fraction of the polymer in the swollen specimen, and χ is the is
HTPB, and the hydroxyl groups in the AEHTPB and HTPB the Flory−Huggins interaction parameter between polymer
molecules can interact through hydrogen bonds, which further and solvent. Vp is computed from
improves the compatibility between AEHTPB and HTPB.
Vp = 1/[1 + (m1/m0 − 1)ρp /ρs ] (2)
3.3. Mechanical Properties. The stress−strain curves of
elastomers with different mass ratios of AEHTPB are exhibited where m0 is the dry weight of the polymer and m1 is the wet
in Figure 5. We can observe that the tensile strength of the weight of the polymer. ρs and ρp are the densities of the solvent
elastomer increases with the AEHTPB content, while the and the polymer, respectively. A value of 0.35 is taken for χ
elongation at break gradually decreases. The elongation at (for HTPB−toluene interaction46). The cross-link density and
break of HTPB elastomer is as high as 1250%, but the tensile corresponding mechanical properties of each elastomer are
strength is only 0.32 MPa. When the addition of AEHTPB is listed in Table 3.
5%, the elongation at break is 997% and the tensile strength is
increased to 0.54 MPa, demonstrating that AEHTPB can Table 3. Cross-Link Network Structure Parameters and
effectively enhance the strength of the binder matrix. It is Mechanical Properties of Different Elastomers
reported that the average functionality of HTPB molecules is
AEHTPB content (wt %) ρp (g/cm3) Me σ (MPa) ε (%)
2.1−2.3,41 which means the cross-link density of the elastomer
prepared from HTPB and IPDI is relatively low. However, 0 0.904 41278 0.32 1225
AEHTPB is a high functionality polymer, which can act as a 1 0.905 39217 0.33 1183
2 0.906 37532 0.34 1155
cross-linking agent during the curing process to increase the
3 0.908 34558 0.37 1103
matrix cross-link density. Meanwhile, the hard segment
4 0.910 27028 0.45 1030
content is increased with increasing AEHTPB. As a result,
5 0.913 22053 0.54 997
the physical cross-link points in the system also increase
10 0.916 17662 0.66 921
accordingly.42 15 0.919 10164 0.92 702
Also, it is worth noting that, when the content of AEHTPB 20 0.922 6317 1.07 458
is low, the impact on the elastic mechanical properties is also 25 0.926 4448 1.06 158
relatively small (Figure 5a). For example, when the addition of
AEHTPB is 3%, the tensile strength of the elastomer is 0.37
Table 3 shows that the cross-link density gradually increased
MPa and the elongation at break is 1103%, which has changed with the increase of AEHTPB, and the changing trend is
little compared with the HTPB elastomer. This is different similar to the mechanical properties. The cross-link network
from the traditional cross-linking agent (such as glycerol); the structure formed by HTPB, AEHTPB, and IPDI is depicted in
addition of the small molecule cross-linking agent is usually Figure 6. Since AEHTPB is a polymer with a large number of
very low (less than 1%).43 hydroxyl groups, it can create highly cross-linked areas in the
3.4. Analysis of Cross-Link Network Structure. The binder network during the curing process. These regions are
macromechanical properties of polyurethane elastomers are composed of very short chains and would not be elastic in
closely related to their microstructures. Here, the swelling comparison with the regular HTPB chains. From the
method was used to determine the cross-link density of the macroscopic view, these short chains in aggregates could be
AEHTPB/HTPB elastomers. The cross-link density of the regarded as large multibranched cross-link points (the red area
polymer is usually characterized by the average molecular in Figure 6). When the amount of AEHTPB added is small,
weight (Me) of adjacent cross-link points, and Me can be these macro-cross-link points are also less, which has little
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Figure 6. Cross-link network structure of HTPB/AEHTPB/IPDI
system, where Nc* is the number of carbon atoms between the cross-
link points.
effect on the cross-link density and mechanical properties of
the elastomer. Only when the addition of AEHTPB reaches a
certain level will the system’s cross-link density increase
significantly.
To evaluate the hypothesis discussed above, we prepared
AEHTPB15%/HTPB and AEHTPB20%/HTPB elastomers
under the same conditions and tested their mechanical
properties. The addition amounts of AEHTPB20% (hydroxyl
value = 2.721 mmol/g) and AEHTPB15% (hydroxyl value =
2.252 mmol/g) were 10 and 13.2%, respectively, to ensure that
the total number of hydroxyl groups in their AEHTPB/HTPB
mixture and the amount of curing agent added were the same
(R(NCO/OH) = 1.0). Table 4 tabulates the test results of
Table 4. Cross-Link Density and Mechanical Data Observed
for AEHTPB15%/HTPB and AEHTPB20%/HTPB Elastomers
AEHTPB content
sample (wt %) Me σ (MPa) ε (%)
AEHTPB15/HTPB 13.2 11611 0.87 714
AEHTPB20/HTPB 10 15780 0.69 885
cross-link density and mechanical properties. As we can see,
the cross-link density and tensile strength of the AEHTPB15%/
HTPB elastomer are higher than those of AEHTPB20%/HTPB.
Therefore, we can conclude that the content of AEHTPB is the
main factor affecting the mechanical properties of AEHTPB/
HTPB elastomer, not the degree of modification.
3.5. Effect of AEHTPB on AP Thermal Decomposition.
The TG−DSC thermal analysis method was applied to
investigate the effects of HTPB and AEHTPB on the thermal
decomposition performance of AP. Figure 7 displays the
thermal decomposition curves of pure AP, HTPB, AEHTPB,
HTPB/AP (by mixing in a mass ratio of 2:8), and AEHTPB/
HTPB/AP (by mixing in a mass ratio of 1:19:80), respectively.
In addition, the thermal decomposition performances of RDX,
HTPB/RDX, and AEHTPB/HTPB/RDX are provided in the
Supporting Information.
It can be seen from Figure 7a that the thermal
decomposition of pure AP presents three stages: the first
stage occurs at 246.8 °C, which represents the crystal structural
transition from orthorhombic to cubic without mass loss.18 In
the second stage, the exothermic peak at 317.7 °C is attributed
to low-temperature decomposition and accompanied by 19.9%
mass loss.47 According to the mechanism of the thermal
decomposition of AP, the low-temperature-decomposition
(LTD) step is a solid−gas multiphase reaction, including
decomposition and sublimation:
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NH4ClO4 (s) ⇆ NH3(s) + HClO4 (s) (3)
In the third stage (the high-temperature decomposition
(HTD)), the exothermic peak appears at a relatively higher
temperature of 440.6 °C, and this corresponds to the complete
decomposition of AP.48 In this process, the adsorbed NH3 and
HClO4 are gradually desorbed into gaseous molecules, and the
redox reactions can take place under a certain temperature:
NH4ClO4 (s) → NH3(g) + HClO4 (g) → O2 (g) + N2(g)
+ Cl 2(g) + H 2O(g) (4)
Parts b and c in Figure 7 are the TG−DSC curves of HTPB
and AEHTPB, respectively. The results show that the thermal
decomposition of HTPB has mainly gone through two stages.
For the first stage, the exothermic peak is about 371.5 °C and
is accompanied by 21.3% mass loss. The reactions are primarily
depolymerization, cyclization, and cross-linking, accompanied
by partial decomposition of the cyclized product.49 The second
stage is an endothermic process, with the endothermic peak at
485 °C and with rapid mass loss. This stage primarily involves
the decomposition of the cyclized product with increasing
temperature. Similarly, the thermal decomposition of AEHTPB
also involved two stages. The first exothermic peak around
364.9 °C corresponds to 39.9% weight loss. We could find that
the initial decomposition temperature of AEHTPB is lower
than that of HTPB, and the weight loss is higher. The main
reason is that the thermal degradation activation energy of the
C−N bonds and C−O bonds in the AEHTPB molecule is low
and the molecule is easier to decompose.
Figure 7d,e illustrates the TG−DSC curves of HTPB/AP
and AEHTPB/HTPB/AP. In Figure 7d, the crystallographic
transition temperature and the LTD exothermic peak temper-
ature in the HTPB/AP mixture system are 248.6 and 316.4 °C,
respectively, which are the same as those of pure AP.
Surprisingly, the HTD exothermic peak of AP shifted from
440.6 to 407.5 °C. The reason is as follows: when the
temperature is lower than the first exothermic peak temper-
ature of HTPB (371.5 °C), the HTPB is relatively stable, so
AP would not be exposed. As the temperature continues to
rise, HTPB begins to rapidly decompose and exposes AP.
More importantly, at this time the temperature has exceeded
the first exothermic peak temperature of AP, causing
accelerated decomposition of AP and instant release of a
large amount of energy, and it advances the high-temperature
decomposition of AP. For the AEHTPB/HTPB/AP mixture
system, the same endothermic peak at 248 °C is also found.
However, the exothermic peak of LTD rises to 337.5 °C, which
is nearly 20 °C higher than that of pure AP, and the
exothermic peak area is reduced. Moreover, the exothermic
peak of HTD has no change compared with the HTPB/AP
mixture system. From the above results, it can be seen that the
addition of AEHTPB effectively inhibited the low-temperature-
decomposition process of AP. Accordingly, in combination
with all our observations, we put forward the mechanism of
inhibiting the decomposition of AP: First, the AEHTPB
molecule contains tertiary amine groups, which can react with
the surface of AP particles to form ammonium salt ion bonds
and release ammonia.50,51 The reaction formula is as follows:
(CH3CH 2)2 NR + NH4ClO4
→ (CH3CH 2)2 RN+HClO4 − + NH3↑ (5)
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Figure 7. TG−DSC curves of (a) pure AP, (b) pure HTPB, (c) pure AEHTPB, (d) HTPB/AP mixture, and (e) AEHTPB/HTPB/AP mixture in
nitrogen atmosphere.
In the meantime, the AEHTPB molecules are firmly
adsorbed on the AP surface by the bonding effect of ionic
bonds, forming a dense coating layer, and this transition layer
temporarily prevents the buildup of a perchloric acid shell on
the AP surface during LTD (that is, inhibits the desorption of
NH3) (Figure 8). By contrast, the interfacial interaction
between HTPB and AP is weak, and the relatively loose
adsorption layer formed by the HTPB cannot prevent the
desorption of ammonia.
To further explore the effect of AEHTPB on reducing the
burning rate of the propellant, we applied AEHTPB to the
HTPB propellant and tested the burning rate. Table 5 presents
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the burning rates of propellants with different contents of
AEHTPB. The results show that AEHTPB can effectively
reduce the burning rate of HTPB propellant. In the presence of
5 wt % AEHTPB, the propellant burning rate could decrease
from 8.54 to 7.62 mm/s, dropping by 10.8%. However, as the
content of AEHTPB increases, the burning rate of the
propellant no longer changes significantly. According to the
mechanism of AEHTPB, we can speculate that, when the
content of AEHTPB is 5 wt %, the AP particles in the
propellant have been completely coated. Therefore, continuing
to increase the amount of addition will not have a better
reduction effect.
https://dx.doi.org/10.1021/acs.iecr.0c06172
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Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

MPa, ε = 51.9%), indicating that AEHTPB has the interface

bonding effect and can improve the mechanical strength of the
propellant.
Furthermore, to understand the bonding effect of AEHTPB
on different fillers, we prepared propellant samples containing
a single solid filler and studied them through scanning electron
microscopy (SEM) and mechanical testing. The mechanical
properties and SEM images are shown in Table 6 and Figure

Table 6. Mechanical Properties of Single Filler Samples with

and without AEHTPB

Figure 8. Schematic diagram of the mechanisms of AEHTPB tensile strength elongation

fillera binderb (MPa) (%)
inhibiting AP thermal decomposition.
AP (50 wt %) HTPB 0.57 54.5
Table 5. Burning Rates and Pressure Exponents of (D50 = 121.37 μm) AEHTPB/HTPB 0.96 102.6
Propellants with Different Contents of AEHTPB RDX (50 wt %) HTPB 0.69 46.4
(D50 = 25.11 μm) AEHTPB/HTPB 0.78 54.9
burning rate (mm/s) Al (50 wt %) HTPB 1.40 255.2
AEHTPB content (D50 = 7.12 μm) AEHTPB/HTPB 1.61 280.6
(wt %) 3.5 MPa 5.5 MPa 7.5 MPa 9.5 MPa n a
Weight percent relative to overall sample. b
The mass ratio of
0 5.53 6.71 7.69 8.54 0.436 AEHTPB to HTPB is 1:19.
5 5.03 6.06 6.90 7.62 0.415
10 4.99 6.02 6.84 7.55 0.413
15 4.97 6.02 6.82 7.53 0.413
10. The tensile testing results indicate that, even without
3.6. Interfacial Bonding Effect of AEHTPB. As AEHTPB, the sample of HTPB/Al can obtain good
mentioned above, AEHTPB molecules can be adsorbed on mechanical properties, but the testing results of HTPB/AP
the AP surface through ionic bonds and form a dense coating and HTPB/RDX systems are not satisfactory. After the
layer. During the curing process of the propellant grains, the addition of AEHTPB, the mechanical properties of the
hydroxyl groups in the AEHTPB molecules can react with the AEHTPB/HTPB/Al system are further improved. Also, both
curing agent and connect to the binder matrix network. Thus, the tensile strength and the elongation at break of the
AEHTPB should has an interface bonding function in the AEHTPB/HTPB/AP system are significantly increased,
propellant.52 To examine the practical effect, some propellant especially the elongation at break, which increased from 54.5
level studies were conducted. The propellant used a mixture of to 102.6%. However, the improvement of the AEHTPB/
AEHTPB/HTPB as a binder (AEHTPB content is 5 wt %), HTPB/RDX system is not evident. On the basis of the above
with AP, RDX as the oxidizer, and aluminum powder as analysis, we can draw the following conclusions: (1) The
metallic fuel. For comparison, the performance of the adhesion of AP and binder matrix as well as RDX and binder
propellant processed with HTPB−IPDI polyurethane as a matrix are the main factors that affect the mechanical
binder was also evaluated. properties of propellant. (2) AEHTPB has a significant
Figure 9 displays the maximum tensile strength (σ) and the bonding effect on AP particles, but the bonding effect on
elongation at break (ε) of propellant. As shown, the RDX particles is relatively smaller.
mechanical properties of propellants based on the AEHTPB/ Figure 10 displays the images of filler particles and fracture
HTPB binder system are superior to those in HTPB surface of the propellant samples with and without AEHTPB.
propellant. The tensile strength of the AEHTPB/HTPB As depicted in Figure 10e, a large number of AP particles are
propellant is 0.95 MPa and elongation at break is 70.1%, exposed at the fracture surface and not covered by the binder.
which are higher than those for HTPB propellant (σ = 0.65 After the addition of AEHTPPB (Figure 10i), the fracture
surface of the propellant becomes smooth and the exposed AP
particles are invisible, indicating that the interface between AP
and binder matrix is firmly bonded and the fracture process is
mainly internal tearing of the binder matrix. Since both HTPB
and AEHTPB molecules lack functional groups that can
interact with RDX,53,54 samples containing RDX have poor
adhesion between the filler and the adhesive matrix (Figure
10f,g). Typically, metal fillers show strong interaction with the
binder matrix because of its larger specific surface area and
ability to form coordination bonds with electronegative atoms
in the binder matrix (such as N and O atoms), which is much
stronger than van der Waals interaction.55,56 As expected, the
Al powders in Figure 10g−l are all completely covered by the
bonding matrix, and no interface peeling occurs. The SEM
Figure 9. Maximum tensile strength (σ) and maximum elongation (ε) observation results are consistent with the mechanical
of propellant. properties.
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Industrial & Engineering Chemistry Research
Figure 10. SEM images of (a) AP, (b) RDX, and (c, d) Al powder. Fracture surfaces of propellant samples of (e) HTPB/AP, (f) HTPB/RDX, (g,
h) HTPB/Al, (i) AEHTPB/HTPB/AP, (j) AEHTPB/HTPB/RDX, and (k, l) AEHTPB/HTPB/Al.
4. CONCLUSIONS
Starting from commercial HTPB, multiamine, hydroxy
polybutadiene (AEHTPB) was synthesized through chemical
modification. FTIR and NMR data have confirmed the
modification was successful, and we also determined
physicochemical properties, such as viscosity, hydroxyl value,
amine value, and Tg. The results showed that 15% modification
on the HTPB backbone gives a balance of a different
performance, and the product exhibits good compatibility
with HTPB. Then, we prepared the elastomer by using a blend
of AEHTPB and HTPB, and the results demonstrate that the
introduction of AEHTPB can effectively enhance the
mechanical strength of the elastomer. The TG−DSC thermal
analysis study proves that AEHTPB could inhibit the low-
temperature decomposition of AP. Furthermore, studies of the
propellant level were conducted, and the propellant based on
the AEHTPB/HTPB mixture binder provides mechanical
properties superior (35.1−46.2%) to those of the HTPB
propellant, and the burning rate was 10.8% lower than that of
the HTPB propellant. Finally, tensile testing of single
component propellant and observation of fracture surface
morphology further indicate that AEHTPB has a significant
bonding effect on AP particles, but it is inefficient for RDX due
to the lack of functional groups that interact with RDX. The
results have shown a high application potential of the proposed
modified products in AP-based propellants, and it also points
out the direction for subsequent research work.
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■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.iecr.0c06172.
13
C NMR spectra of HTPB, EHTPB, and AEHTPB; δ
assignment from 1H NMR of HTPB, EHTPB, and
AEHTPB; effect of reaction time on double bond
conversion rate and calculation equation of double bond
conversion; TG−DSC curves of RDX, HTPB/RDX
mixture, and AEHTPB/HTPB/RDX mixture in nitrogen
atmosphere; burning rates and pressure exponents of
propellants with different contents of AEHTPB (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Xilong Zhang − Hu Bei Sanjiang Aerospace Jianghe Chemical
Technology Co., Ltd., Yichang 444200, People’s Republic of
China; Email: zhangxilong@hnu.edu.cn
Jianru Deng − College of Chemistry and Chemical
Engineering, Hunan University, Changsha 410082, People’s
Republic of China; orcid.org/0000-0002-1386-3062;
Email: dengjianru@hnu.edu.cn
Authors
Pingan Zhang − College of Chemistry and Chemical
Engineering, Hunan University, Changsha 410082, People’s
Republic of China
Wenjiayi Tan − College of Chemical Engineering and
Materials Science, Tianjin University of Science and
Technology, Tianjin 300222, People’s Republic of China
https://dx.doi.org/10.1021/acs.iecr.0c06172
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Industrial & Engineering Chemistry Research
Juan Chen − College of Chemistry and Chemical Engineering,
Hunan University, Changsha 410082, People’s Republic of
China
Jianmin Yuan − College of Material Science and Engineering,
Hunan University, Changsha 410082, People’s Republic of
China; orcid.org/0000-0002-8250-8363
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.iecr.0c06172
Notes
The authors declare no competing financial interest.
■
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