Indones. J. Chem.

, 2020, 20 (2), 919 - 928 919

Kinetic Study of HTPB (Hydroxyl Terminated Polybutadiene) Synthesis

Using Infrared Spectroscopy

Heri Budi Wibowo1,*, Widhi Cahya Dharmawan1, Ratih Sanggra Murti Wibowo2, and Adi Yulianto2
1
Indonesian National Institute of Aeronautics and Space – LAPAN, Jl. Pemuda Persil No. 1, Jakarta 13220, Indonesia
2
Faculty of Engineering, Universitas Gadjah Mada, Jl. Grafika No. 2, Yogyakarta 55281, Indonesia

* Corresponding author: Abstract: A kinetic study of HTPB synthesis by radical polymerization of butadiene with
hydrogen peroxide initiator was conducted using infrared spectroscopy. HTPB conversion
email: heribw@gmail.com
was determined based on the conjunction termination rate constant, and all
Received: September 21, 2019 polymerization kinetics were evaluated to identify the constant. All polymerization steps
Accepted: December 16, 2019 (decomposition, initiation, propagation, conjunction, and proportional termination) can
DOI: 10.22146/ijc.49863 be evaluated based on polymer conversion and functionality from data provided by
infrared spectroscopy. The investigation variables included the initial molar ratio of
initiator to monomer (H2O2/butadiene) and the reaction temperature. These steps were
assumed as the first-order reactions, giving constant reaction rates of kd, ka, kp, kt, ktc, and
ktd. The reaction rates obtained for these constants were 4.2 × 10–5 sec–1, 8.9 × 10–4, 7.7 ×
103, 8.5 × 107, 3.2 × 107 and 5.3 × 107 L mol–1 sec–1, respectively, with activation energy of
7608, 14188, 2247, 105, 87 and 135 kJ mol–1, respectively. The determining step of the
reaction rate was identified as the initiation reaction. HTPB conversion can be measured
if all polymerization kinetics constants have been evaluated.

Keywords: polymerization; HTPB; butadiene

■ INTRODUCTION substituted HTPB with nitro, azide, and oxy functional

groups [4-7]. HTPB is a polybutadiene with two chains
Polyurethane based on hydroxyl-terminated
of hydroxyl groups that have been particularly studied in
polybutadiene (HTPB), in recent years, has been used as a
its use in propellant materials. HTPB can be synthesized
solid propellant binder for satellite-launcher-motor
by ionic, ionic-coordination, and radical polymerization
boosters and ICBM (intercontinental ballistic missile)
of butadiene. HTPB produced by ionic and ionic-
motors [1-2], because it has good mechanical properties
coordination polymerization has narrow molecular
at rocket operating temperatures. Polyurethane based on
distribution weight, but this type of production requires
HTPB is synthesized by copolymerization of HTPB and
a highly complex reaction, which is expensive to carry
isocyanates, such as toluene diisocyanate (TDI) or
out [3-5]. In contrast, HTPB produced by radical
isophorone diisocyanate (IPDI). Research into
polymerization has broad molecular weight distribution,
polyurethane based on HTPB as a propellant binder has
but its formation reaction is simple and cheap. HTPB is,
been conducted since 1945 [3]. Initially, this research
therefore, generally produced by radical polymerization
focused on HTPB/isocyanate composition related to its
of butadiene using a hydrogen peroxide initiator [3,8].
mechanical and viscous-elasticity properties. Subsequent
The synthesis mechanism for HTPB by radical
research has focused on the effect of HTPB structures
polymerization of butadiene with hydrogen peroxide
such as chain length, isomers, hydroxyl value, and
initiator is (1) decomposition of hydrogen peroxide
molecular weight distribution. In the last ten years,
producing hydroxyl radicals, (2) monomer initiation by
research into polyurethane based on HTPB has looked at
hydroxyl radicals producing radical monomers, (3)
increasing the energetic properties of the binder by
propagation of radical monomer growth with

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920 Indones. J. Chem., 2020, 20 (2), 919 - 928

monomers producing radical polymers, (4) termination infrared spectrometry, based on double bond absorption
of radical polymers producing ‘dead polymers’ [9-10]. and type of isomer (cis, trans and vinyl isomers)
Termination steps are simultaneous mechanisms [12,14,19]. Kinetic study of HTPB synthesis by infrared
involving both conjunction and disproportional spectroscopy is the most commonly used method
reactions. Conjunction termination would produce because it is fast, cheap and simple to perform.
HTPB, while disproportional termination would produce Infrared spectrometry using adsorption infrared
mono hydroxyl polybutadiene (HPB) [4]. Given this spectra at wavenumber 2250 cm–1 can be applied to
mechanism, the study of the kinetics of HTPB synthesis determine hydroxyl value and functionality of
requires at least two data sets to be retrieved. The polybutadiene and HTPB [20-22]. The functionality of
initiation and termination steps are fast reactions [8], and HTPB is a ratio of average hydroxyl chain to
data kinetics are limited by polymer weight and average polybutadiene structure. Based on this functionality, the
molecular weight. Therefore, the difficulty is encountered ratio of mono hydroxyl polybutadiene and hydroxyl
in data retrieval, given the fast reaction rate of the process. terminated polybutadiene (HTPB) can be estimated and
For this reason, it is assumed that in the kinetics of HTPB infrared analysis of polybutadiene can be used to
synthesis, termination and initiation rates are the same, determine the extent of reaction and functionality. All of
and simultaneous conjunction and disproportional the constant reaction steps in HTPB synthesis should be
termination are ignored [10]. evaluated using at least two kinetic data items, and this
This approach resembles the olefin polymerization research, therefore, includes the conjunction and
kinetics for rubber applications [7-8]. The kinetic of disproportional steps in studying the kinetics of HTPB
radical polymerization of butadiene and other diene synthesis via infrared spectroscopy to describe HTPB
compounds and olefins for rubber applications has been conversion, average functionality, and molecular weight
explored since 1940 [11-12]. The polybutadiene in rubber distribution. Through this approach, all kinetic data for
applications has hydrogen-ended functional groups, and HTPB synthesis can be explored.
polymerization usually uses a peroxide initiator, a redox In HTPB synthesis by radical polymerization of
system, and other strong oxidizers. Wibowo assumes that butadiene using a hydrogen peroxide initiator,
the ratio of HTPB and mono hydroxyl polybutadiene butadiene is radically polymerized via initiation,
(HPB) conversion is constant, but this data cannot be propagation and termination stages [6-7]. The initiation
satisfied statically [13]. The aim of this research is to stage involves the dissociation of hydrogen peroxide
explore all the kinetic steps of HTPB synthesis using at (H2O2) to produce hydroxyl radicals (OH•) which then
least three sets of data retrieved in a manner suitable for react with t monomer butadiene (C4H6), producing
fast reaction rates. radical monomer chains with hydroxyl groups (HO–
The kinetics of radical polymerization can be C4H6•). The propagation stage involves the growth of the
evaluated based on the presence of increased polymers or polymer. The active radical monomers (HO–C4H6•)
decreased monomers. Decreased monomers can be react with other monomers to produce radical active
observed from their pressure [14-15], while increased dimers (HO–(C4H6)2•). Polymer activity develops by the
polymers can be evaluated from their weight and chain addition of monomer butadiene to produce higher
extent or molecular weight. Unfortunately, decreased polymer radical actives (HO–(C4H6)n•). The growth
monomers and increased polymers cannot be activity of the polymer radicals is terminated by
simultaneously identified. The polymer molecular weight reactions between polymer radicals producing dead
can be evaluated via colligative property measurement, polymers, via the active polymer radical (HO–(C4H6)x)
viscosity, light scattering, size exclusion chromatography reacting with the other active radical polymers (HO–
and gel permeation chromatography [16-18]. The (C4H6)y•). The termination can proceed by
polymer extent of a reaction can also be identified by combinatorial-type reactions producing HTPB with two

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 Indones. J. Chem., 2020, 20 (2), 919 - 928 921

end hydroxyl chains (HO–(C4H6)x+y-OH) or vibrations (wagging) of the CH groups, then

proportional-type reactions producing two dead extrapolated to a standard curve using Beer’s law [12].
polymers, HO–(C4H6)x and HO–(C4H6)y, with one of the The standard solution was HTPB in toluene at
dead polymers having a double bond. Functionality is concentrations of 1.0 × 10–5, 5.0 × 10–5, 1.0 × 10–4, 5.0 ×
identified as the total of dead polymers of both two- 10–4 and 1.0 × 10–3 mol L–1.
hydroxyl-chained (HTPB) and one-hydroxyl-chained The hydroxyl number of HTPB was determined by
(mono hydroxyl polybutadiene) types. Based on the observing FTIR uptake values at wavenumber 3450 cm–1
enthalpy of formation, disproportional-type reactions as specific uptake for hydroxyl groups [1]. The
need higher energy than combinatorial-type reactions [8- absorbance of hydroxyl groups was then extrapolated
9]. By means of this kinetic model, all of the kinetic data with standard alcohol 1,4-butanediol and 1-butanol. In
(rate constants), including the combinatorial and this research, standard alcohol was a mixture of 1,4-
proportional steps, can be effectively evaluated. butanediol and 1-butanol (mol/mol) at 1.0, 1.1, 1.2, 2.0.
The functionality of 1-butanol is 1 and 1,4-butanediol is
■ EXPERIMENTAL SECTION
2.
Materials
Procedure
Butadiene 98% used in this research was produced
Butadiene was reacted with hydrogen peroxide in
by Aneka Gas Co Ltd., Jakarta, Indonesia and was distilled
a 1-L autoclave for 60 min in inert nitrogen conditions.
to remove tert-butylcatechol. The hydrogen peroxide
The reaction was isothermal and conducted at 100 °C
used was in pure analysis grade, and the solvent used was
and 25 bar pressure. The extent of the reaction and
toluene.
functionality was measured by FTIR spectroscopy at
Instrumentation wavenumber of 3450, 730, 790 and 910 cm–1 [1,4,7].
The reactor used was an autoclave of 1-L capacity Reaction parameters were initiator and reaction
equipped with a stirrer and hot fluid control. A closed temperatures.
FTIR cuvette was connected to the reactor and the The effect of the initiator on polymerization
solution from the reactor was continuously circulated to kinetics was studied by adjusting the initial
it. H2O2/butadiene ratio (mol/mol) to 10, 20, 30 and 32%,
The in-situ HTPB product was identified by FTIR and the reaction was carried out at 100 °C, 25 bar, and
(Fourier transform infrared spectrometry). FTIR outputs stirrer speed of 100 rpm. The initial butadiene
were measured at ambient conditions at the wavenumber concentration was 1 M. The effect of reaction
range of 400–4000 cm–1 using an FT-IR spectrometer temperature on polymerization kinetics was studied by
(Prestige-21). HTPB was identified at wavenumber of adjusting the reaction temperature to 100, 110 and 118 °C
3500, 1700, 710, 790, and 910 cm–1 for specific absorption at a pressure of 25 bar, initial H2O2/butadiene ratio of
of hydroxyl and CH, and cis, trans and vinyl isomers [6]. 10%, and stirrer speed of 100 rpm.
HTPB was observed for absorption bending vibrations Kinetic model
(wagging) of the CH groups in the cis-HTPB unit at a The polymerization of butadiene with hydrogen
wavenumber of 730 cm–1, for out-of-plane (wagging) peroxide initiator occurs through free radical
vibrations of the CH2 groups near the double bond of the mechanisms [8]. The reaction is started by the
vinyl-HTPB units at 910 cm–1, and for out-of-plane dissociation of hydrogen peroxide to form a pair of
(wagging) vibrations of the CH groups near the double hydroxyl radicals (OH•) with dissociation rate constant
bonds in trans-HTPB units at 970 cm–1. of kd. The reaction of hydroxyl radical (OH•) and
The polymer concentration was measured for monomer butadiene (H2C=CH–CH=CH2) produces the
absorbance at wavenumber 1750 cm–1 via bending radical-ended monomer •H2C–CH=CH–CH2OH with

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922 Indones. J. Chem., 2020, 20 (2), 919 - 928

adding monomer reaction rate of ka. The initiation step, constant is ka, the propagation rate constant is kp and the
therefore, comprises the dissociation of hydrogen termination rate constant is kt. The combinatorial
peroxide and the adding of monomer reaction. The reaction rate constant in the termination reaction is ktd
propagation reaction is started by radical-ended dimer and the disproportional reaction rate constant in the
•
(H2C–CH=CH–CH2)2OH production from radical- termination reaction is ktd. These polymerization
ended monomer •H2C–CH=CH–CH2OH and another kinetics are the assumed first order:
monomer. The radical-ended dimer then reacts with kd
I → 2R (1)
another monomer to form radical-ended trimer •(H2C–
ka
CH=CH–CH2)3OH. These propagation reactions occur R + A → RP1 (2)
repeatedly so that the radical-ended polymer acquires a kp
longer chain length •(H2C–CH=CH–CH2)xOH. The RPj + A → RPj+1 (3)
propagation rate is constant at steady-state and radical- k tc
ended polymer reactivity in the chain growth is the same. RPi +  RPj  →  Pi + j (4)
Individual propagation reactions are identified as rp1, rp2, k td
RPi +  RPj  →  Pi + Pj (5)
…, rpi, following the extent of the reaction. These
propagation reaction steps have the same reaction rates The reaction rate equation of initiator dissociation
because the activity of the radicals is the same (their is expressed in Eq. (6). The reaction rate equations of the
activity is not affected by the size of the molecule). The polymerization steps (initiation, propagation, and
radical-ended polymer reactivity in chain growth is the termination) are expressed in Eq. (6) to Eq. (10).
same. Therefore, all propagation stages can be Polymer concentration comprises all polymers with
characterized using the same reaction rate constant of kp chain extent from j = 0 to j = n, [P]0 = ∑nj=0 Pj . The active
[8-10]. The termination step occurs in simultaneous radical concentration [M]o comprises all radical
combinatorial and proportional reactions [7]. •H2C– polymers with chain extent from j = 0 to j = n, [M]o =
CH=CH–CH2(H2C–CH=CH–CH2)x-OH and other ∑nj=0 RPj . The termination rate constant is the sum of
polymer-ended radicals produce mono hydroxyl combination and disproportion rate constants (kt = ktc +
polybutadiene with a double bond, H2C–C=H– ktd).
CH=CH2(H2C–C=H=CH–CH2)x–OH, and another d[I]
Rd = − =
2fk d [I] (6)
mono hydroxyl polybutadiene with a single bond H3C– dt
CH=CH–CH2(H2C–CH=CH–CH2)x–OH. The junction d[A]
Ri = − =k a [A][P1 ] (7)
or combinatorial reaction is a covalent bond reaction of dt
d[A]
the radical-ended polymer •(H2C–CH=CH–CH2)x–OH Rp = − =k a [A][P1 ] + k p [A][P]0 (8)
dt
and the other radical-ended polymer •(H2C–CH=CH–
d[P]o
CH2)y–OH to produce HTPB, HO(H2C–CH=CH– =
R ap = R i − 2k a [P]0 (9)
dt
CH2)x+y–OH. The combinatorial and proportional d[M]o
termination rate constants are ktc and ktd. Rt = − = (2k tc + k td) )[P]02 (10)
dt
The initiator decomposition, initiation, propagation Monomer A is initiated by hydroxyl radicals
and termination reactions in the radical polymerization of forming radical-ended monomers followed by
butadiene are simplified as presented in Equations 1 to 5. continuous propagation with polymer radicals growing
Compound I is the initiator, R and A are butadiene their size/length of chain. Through polymer radical
monomers, RPj are active polymers with chain length i, growth, radical concentration is constant (steady-state)
and RPj and RPjR are stable polymers bound to hydroxyl until the rate of radical forming is zero (Rap = 0). Eq. (9)
groups R with chain length j. The initiator decomposition would express in Eq. (11).
reaction rate constant is kd, the monomer adding rate

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 Indones. J. Chem., 2020, 20 (2), 919 - 928 923

 fk [I] 
12 The combinatorial termination rate is the
[P]0 =  d  (11) increasing rate of polymer RMjR expressed by Eq. (19).
 kt 
Eq. (20) is the integration of Eq. (19) with the initial
The equation of propagation rate would be
condition [RMjR]0 = 0 and HTPB concentration at time
expressed by substituting Eq. (11) into Eq. (7) to form Eq.
t of [RMjR].
(12).
d[RMi R]
 kp  = k td [RMi R] (19)
Rp = 
 k1 2 ( )
 fk d [I]1 2 [A] (12) dt
= k t t + cons tan ts
ln[RMi R] (20)
 t 
Eq. (6) is merged with Eq. (9) then integrated with β Eq. (18) is to be substituted into Eq. (20) to form
= (ktc/kt) and α = (-kdt) to express initial monomer Eq. (21), which is the relationship equation of the
concentration [A]o, expressed in Eq. (13) where MA is the polymer produced (HTPB) and the functionality of the
molecular formula of monomer butadiene [11]. polymer as the time of reaction. The disproportional
Monomer conversion is X = [A]/[A]0. termination rate constant ktd is the slope of plotting ln(1
[A]0 = (2 − β)f[I]0 (1 − α) (13) – P/fOH) as time t. The conjunction termination rate
constant ktc is the deviation of kt and ktd (ktc = kt-ktd).
Mn =
([M]0 − [M]) MA (14)  
([P]0 + [M]0 ) ln  1 − P
f =k td t (21)
 OH 
A0 XM A
Mn = (15) The polymer concentration was determined by the
([P]0 + [M]0 ) absorbance of polymers at wavenumber 910 cm–1 at the
Eq. (16) is formed from merging Eq. (10), (12) and time of reaction.
(15) and would apply to the calculation of the termination
rate constant kt. The values of kt and β can be evaluated ■ RESULTS AND DISCUSSION
based on each change of average molecular weight and HTPB was identified by infrared spectroscopy at
weight of the polymer. wavenumber 400–4000 cm–1 and its infrared spectrum is
12 12 shown in Fig. 1. The HTPB compound was identified
 ([A]0 XM A ) / Mn   fk d 
12
 [I] 
 =    + (2 − β)(1 − α)  0  (16) based on infrared absorption at 3450, 1730, 710, 910, and
 [I]0 α   kt   α 
970 cm–1, a specific absorption for the hydroxyl group,
The propagation rate constant kp is calculated from
C–C bond, and C=C bond with cis, trans, and vinyl
Eq. (6). The constant (kp/kt½) is calculated as the slope of
isomers [12-13]. The presence of a hydroxyl group
plotting Rp to Ri or Rp to (fkd[I]0½[A]0).
indicates that the polybutadiene has hydroxyl groups. The
Polymer functionality (fOH) is the equivalent total of
hydroxyl groups bonded in the polymer (polybutadiene).
Polymers are a mixture of mono hydroxyl polybutadiene
(RMi) and hydroxyl terminated polybutadiene (RMiR)
[9]. The functionality of the polymer is expressed in Eq.
(17).

fOH =
( 2[RMi ] + [RMi R]) (17)
([RMi ] + [RMi R])
The total polymer produced is P with P = 2[RMj] +
[RMjR]. RMi is eliminated from Eq. (17) to become Eq.
(18).
P
[RMi ]= 1 − (18) Fig 1. Infrared spectra of polybutadiene
fOH

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924 Indones. J. Chem., 2020, 20 (2), 919 - 928

absorbance at wavenumber 710, 910, and 970 cm–1 were [A]0 = 0.00023 mol L–1 and [I]0 = 0.00002 mol L–1. The
sharp and strong. The absorption at 930 cm–1 implied polymer produced (XMA) was calculated from the
increasing HTPB. The functionality of HTPB was absorbance of the infrared spectra at 1750 cm–1.
observed at wavenumber 3450 cm–1. To study the kinetic model, the ([A]0XMA/Mn)/
The absorbance of polybutadiene infrared spectra ([I]0α)½ was plotted to the (1-α)([I]0/α)½ and expressed
every ten minutes was observed at wavenumber 910 and in Fig. 2 based on Eq. (16). The value of (2-β) is the slope
3450 cm–1 (Table 1). The HTPB concentration was linear of this curve. The value of (fkd/kt)½ is the intercept of this
to absorbance (Beer’s law) [12]. The HTPB concentration curve. The value of β (ktc/kt) and (fkd/kt)½ are 12,001 and
was calculated based on absorbance at 910 cm–1 (A910) using 8.5 × 1 07 mol L–1 sec–1. The value of fkd was calculated
Beer’s law in Eq. (22) [12]. The functionality of the from the decomposition data of hydrogen peroxide in
polymer was measured based on absorbance at 3450 cm–1 the various solvents [17]. The dissociation rate constant
(A3450) using Eq. (23). The Ɛ and b are molar attenuating of hydrogen peroxide in toluene is 4.2 × 10–5 sec–1 [15].
coefficient or absorptivity of the attenuating species and The propagation rate constant kp was calculated
the optical path length, respectively from Eq. (6). The constant (kp/kt½) was calculated as the
A910 slope of plotting Rp to Ri or Rp to (fkd[I]0½[A]0) as
P= (22)
∈b expressed in Fig. 3. The value of (kp/kt½) is 4.62 and the
A value of kp is 7.7 × 103 mol L–1 sec–1.
RMi  = 3450 (23)
∈b The disproportional termination rate constant (ktd)
The HTPB concentration and functionality every is the slope of curve ln(1-P/fOH) as time t as expressed in
ten minutes are shown in Table 1. Initial condition was

Table 1. HTPB concentration and functionality at 100 °C and pressure of 25 bar

Time (min) Absorbance at 910 cm–1 Absorbance at 3450 cm–1 CP (mol L–1) fOH=[RMR]/[RM]
10 0 0 0 1
20 0.23 0.05 0.00023 1.11111
30 0.35 0.16 0.00035 1.35556
40 0.48 0.31 0.00048 1.68889
50 0.58 0.41 0.00058 1.91111
60 0.62 0.42 0.00062 1.93333

Fig 2. Curve ([A]0XMA/Mn)/([I]0α)½ versus (1-α)([I]0/α)½ Fig 3. The curve of Rp to (fkd[I]0½[A]0)

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radicals. When the monomer radical formation reaction is

complete, the growth of the polymer will decrease [16-17].
The (kp/kt½) value of 2.56 indicates that the
propagation rate is faster than the termination rate. On
polymerization, at 100 °C and a pressure of 350 psi the
polybutadiene formed has a long chain. The reaction at
90 °C and a pressure of 350 psi obtained (kp/kt½) = 0.07,
indicating that the polymer is not formed because all of
the growing polymer radicals will directly become dead
polymers. Thus, the requirement for polybutadiene
formation is a minimum temperature of 100 °C at a
pressure of 350 psi.
The value of ktd is higher than ktc indicating that
Fig 4. Plotting ln(1-P/fOH) as time t more HTPB is produced than monofunctional
polybutadiene. The value of ktd/ktc of 1.6 indicates that
Fig. 4. The value of (kt/ktd) is 2.5. The conjunction polymer functionality is 1.6. HTPB formation is faster
termination rate constant ktc is the deviation of kt and ktd. than the formation of mono functional polybutadiene.
The value of kt, ktd, and ktc are 8.5 × 107 mol L–1 sec–1, 3.2 The results show that the functionality of polymer can
× 107, and 5.3 × 107 L mol–1 sec–1. be used to study the termination reactions of both
Based on the radical polymerization mechanism and disproportional and combinatorial termination in the
the value of their rate constant, value of kd = 4.2 × 10–5 sec–1, radical polymerization of butadiene. This result refines
ki = 8.9 × 10–4 L mol–1 sec–1, kp = 7.7 × 103 L mol–1 sec–1, kt = the study of butadiene polymerization kinetics by using
8.5 × 107 L mol–1 sec–1, ktd = 3.2 × 107 L mol–1 sec–1, and ktc = average molecular weight data and conversion based
5.3 × 107 L mol–1 sec–1. The determining polymerization only on the termination rate [15,17].
rate is the lowest step reaction rate. Therefore, the According to Eq. (13) and Fig. 2, the
determining polymerization rate is the initiation reaction polymerization rate (Rp) is directly proportional to exp(-
which has the lowest reaction rate constant (2.5 × 10–4 L kdt/2), [A][I]0½, and kp/kt½. The polymerization rate is
mol–1 sec–1). proportional to exp(-kdt/2) indicating that the
The monomer radical forming rate is faster than the decomposition rate decreases exponentially as more
initiator decomposition (ki > kD) indicating that the initiators are used for polymerization. The
monomer radical forming step determines the initiation polymerization rate is directly proportional to [A][I]0½,
rate. Every hydroxyl radical formed directly reacts with a indicating that the polymerization rate is directly
butadiene monomer to produce a monomer radical. This proportional to the initial initiator and initial monomer
phenomenon corresponds to Flory’s statement that the concentration. The overall polymerization rate is
speed of initiation in radical polymerization is directly proportional to the initial initiator
represented by the reaction of the formation of a radical concentration. This value is the same as that for the
monomer [13,16]. radical polymerization of both olefin and styrene [14].
The kp value is almost equal to ki, indicating a The polymerization rate is proportional to (kp/kt½)
competitive reaction, each forming of a monomer radical indicating that polymerization will occur if the value of
being followed by the growth of the polymer radical. The (kp/kt½) is greater than one, so propagation will take
overall polymerization reaction rate is an exponential place before termination occurs. The calculation results
curve as shown in Fig. 4. Initially, the polymerization show that the value of (kp/kt½) is 2.56, and so maintained
reaction grows rapidly with the formation of monomer polymerization will take place.

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926 Indones. J. Chem., 2020, 20 (2), 919 - 928

Table 2. Polymerization rate constants of HTPB and TDI

Reaction rate constant Initial H2O2/butadiene ratio (%mol/mol)
10% 20% 30% 32%
kd (sec–1) 4.2 × 10–5 4.2 × 10–5 4.2 × 10–5 4.2 × 10–5
ka (L mol–1 sec–1) 8.9 × 10–4 8.9 × 10–4 8.9 × 10–4 8.9 × 10–4
kp (L mol–1 sec–1) 7.7 × 103 7.7 × 10 3
7.7 × 103 7.7 × 103
kt (L mol–1 sec–1) 8.5 × 107 8.5 × 10 7
8.5 × 107 8.5 × 107
ktc (L mol–1 sec–1) 5.3 × 107 5.3 × 107 5.3 × 107 5.3 × 107
ktd (L mol–1 sec–1) 3.2 × 107 3.2 × 10 7
3.2 × 107 3.2 × 107

Effect of Initiator
The reaction rate constants kd, ka, kp, kt, ktc, and ktd
were calculated using Eq. (16) for different initial
H2O2/butadiene ratios and the results are presented in
Table 2. These results indicate that there is no difference
in the polymerization rate if the polymerization steps are
the same and that the different initial H2O2/butadiene
ratio does not change the polymerization rate constants of
each step. Based on the calculation of the values of kd, ka,
kp, kt, ktc, and ktd, the developed kinetic model had an
average error of 1.9% in comparison to experimental data,
so the model represents real kinetics for different initial
H2O2/butadiene ratios. Therefore, the increasing initial
concentration of the initiator significantly increases the Fig 5. The plot of ln(k) versus 1/T
reaction rate.
Table 3. The activation energy for polymerization of
Effect of Reaction Temperature butadiene
Reaction temperature significantly affects Reaction steps Ea (kJ/mol)
polymerization, following the Arrhenius equation, as Dissociation 7608.1414
Initiation 14188.6724
presented in Eq. (14). The effect of reaction temperature
Propagation 2247.2742
on polymerization rate constants can be evaluated based
Termination 105.5878
on collision frequency factor and reaction activation Conjunction termination 87.2970
energy. To calculate these variables, polymerization of Disproportional termination 135.5182
butadiene was conducted at various reaction temperatures
(100, 110 and 118 °C). After reaction rate constants were identified as the most sensitive to the change of reaction
calculated, ln(ki) was plotted versus (1/T), as can be seen temperature and is, therefore, the determining reaction.
in Fig. 5. According to the Arrhenius equation, the This data confirms that the rate of reaction was affected
intercept is ln(A) and the slope is (-Ei/R). The collision by the reaction temperature increase.
frequency factor and reaction activation energy for each
■ CONCLUSION
reaction rate constant is presented in Table 3.
The activation energy of each reaction step shows the The termination of radical polymerization of
effect of reaction temperature on the reaction rate constant. butadiene using hydrogen peroxide initiator was
The initiation reaction needs higher energy than the other examined by observing the increase of polymer
reactions. Based on Table 3, the initiation reaction can be conversion and functionality. Polymerization of

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 Indones. J. Chem., 2020, 20 (2), 919 - 928 927

butadiene was carried at an initial H2O2/butadiene ratio of Polym. Test., 29 (4), 513–519.
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■ ACKNOWLEDGMENTS
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