European Polymer Journal 49 (2013) 10071016

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European Polymer Journal

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Kinetics and mechanism of grafting styrene onto natural rubber

in emulsion polymerization using cumene hydroperoxide
tetraethylenepentamine as redox initiator
Karnwadee Songsing, Terdthai Vatanatham, Nanthiya Hansupalak
Department of Chemical Engineering, Faculty of Engineering, Kasetsart University, Bangkok, Thailand

a r t i c l e i n f o a b s t r a c t

Article history: Styrenenatural rubber (NR) graft copolymerization using emulsion polymerization with
Received 26 April 2012 cumene hydroperoxide (CHPO)tetraethylenepentamine (TEPA) as redox initiator was
Received in revised form 20 January 2013 investigated. Instead of an equimolar ratio, the optimal molar ratio of CHPO and TEPA
Accepted 22 January 2013
was 1:4, probably due to the compensation for TEPA loss in chain transfer reactions. The
Available online 9 February 2013
rate of copolymerization in terms of initiator and emulsier concentrations, derived from
reviewing of the mechanism of the copolymerization covering reactions in both rubber
Keywords:
particles and micelles, agreed well with experimental data. Its greater dependences on ini-
Emulsion polymerization
Grafting
tiator and emulsier than those in the SmithEwart theory were contributed from the NR
Polystyrene addition, which was conrmed by performing styrene polymerization (keeping all ingredi-
Rubber ents amounts constant, but without NR). The rate of homopolymerization was dependent
Copolymers on the initiator and emulsier to the powers of 0.43 and 0.61, respectively, which was in
good agreement with the theory.
2013 Elsevier Ltd. All rights reserved.

1. Introduction mechanical properties of NR stem from the presence of

Thailand is ranked as the fourth largest producer of nat-
ural rubber (NR) in the world, and thus the Thai Govern-
ment promotes rubbers usage in terms of making higher
value-added products and expanding its range of applica-
tion [1]. One way to expanding rubbers usage is to im-
prove its mechanical properties, which can be done by
grafting vinyl monomer with better mechanical properties
onto NR [2]. Examples of vinyl monomers frequently used
for grafting onto NR are methyl methacrylate (MMA) and
styrene. In addition to the inclusion of vinyl polymer with
better mechanical properties in NR matrix, the improved
Corresponding author. Address: Center of Excellence for Petroleum,
Petrochemicals and Advanced Materials, Department of Chemical Engi-
neering, Faculty of Engineering, Kasetsart University, Bangkok, Thailand.
Tel.: +66 2579 2083; fax: +66 2561 4621.
E-mail addresses: g51650109@ku.ac.th (K. Songsing), fengttv@ku.ac.th
(T. Vatanatham), fengnyh@ku.ac.th (N. Hansupalak).
graft copolymer of the vinyl monomer and NR being able
to reduce interfacial energy between the polymer and the
rubber phases and the domain sizes of those phases [3].
Graft copolymerization between rubber and vinyl
monomer is usually conducted using free-radical emulsion
polymerization, in which an initiator utilized in the poly-
merization is either a redox initiator or thermal initiator
[49]. However, since most redox initiators are insensitive
to oxygen and can work well at high pH, they are more
suitable for polymerizations involving NR latex with
ammonia added for preservation purposes [10]. In addi-
tion, the polymerization using a redox initiator can occur
at low temperatures, leading to lower energy cost and less
chance of the occurrence of depolymerization [11].
A redox initiator is composed of two components: a
hydrophobic oxidizing agent and a hydrophilic reducing
agent, such as benzyoyl peroxideN,N0 -dimethylaniline,
cumene hydroperoxide (CHPO)tetraethylene pentamine
(TEPA), and tert-butyl hydroperoxide (TBHPO)TEPA

0014-3057/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.eurpolymj.2013.01.027
1008 K. Songsing et al. / European Polymer Journal 49 (2013) 10071016

[1215]. Kochthongrasamee et al. found that, comparing to Table 1

other redox initiators (i.e., TBHPOTEPA and K2S2O8 Recipes for emulsion graft copolymerization.

Na2S2O3 initiators), CHPOTEPA initiator is the best redox Organic component (g) 100
system for the graft copolymerization of methyl methacry- Styrene (g):NR (g)a 23:77
late (MMA) onto NR latex because of the highest solubility Deionized water (pph)b 300
Isopropanol (pph)b 7.60
in the oil phase of CHPO, which gives the highest grafting Emulsier (pph)b 0.87, 1.12, 1.30, 1.55
efciency [8]. TEPA (pph)b 0.27, 0.37, 0.45, 0.54
In the literature, most authors report the study of the CHPO (pph)b 0.06, 0.08, 0.10, 0.11
styreneNR graft copolymerization using emulsion poly- Hydroquinone (pph)b 1.70
Reaction temperature (C) 40
merization (with either a thermal initiator or a redox initi-
ator) in terms of inuences of reaction conditions (e.g., a
The weight of NR mentioned in the ratio is the weight of dried rubber
reaction time and temperature and concentrations of content in fresh NR latex.
b
pph = Parts per hundred (of the organic component).
monomers and initiators) on monomer conversion, graft-
ing efciency, graft yield, and mechanical properties
[7,1619]. As there are no papers exploring the kinetics
of the styreneNR graft copolymerization using emulsion
the mixture was stirred for another 15 min before being
copolymerization and CHPOTEPA initiator in terms of
transferred to 30 mL bottles with caps on. Each bottle was
polymerization rate and its dependence on initiator and
then immersed in a hot-water bath controlled at 40 C and
emulsier concentrations, this work can be considered as
afterwards collected at different reaction times. Immedi-
the rst one. The suitable ratio of CHPO to TEPA for the
ately, the liquid in each bottle was transferred to a container
graft copolymerization and the rate of the graft copolymer-
containing hydroquinone to stop the polymerization. The
ization in terms of the initial rate as a function of initial
weight of each sample was recorded before and after drying
concentrations of initiator and emulsier were studied. In
in a conventional oven at 60 C for 24 h and in a vacuum
addition, exponents of initiator and emulsier initial con-
oven at 60 C until no weight change was observed. The
centrations of the rate of emulsion polymerization of sty-
dried product is called PS-graft-NR.
rene initiated by nonequimolar CHPOTEPA initiator
The monomer conversion was determined by gravimet-
were examined to observe the effect of NR by keeping all
ric method. The morphology of PS-graft-NR was investi-
ingredients amounts constant, except NR amount. Fur-
gated under a JEM-2100 transmission electron
thermore, this work investigated the morphology of
microscope (TEM) with specimen heating holder (up to
graftrubber particles. It should be noted that the poly-
800 C) and negative staining with osmium tetroxide
merization rate obtained from this work, which is easily
(OsO4).
conducted, easily applied in industry, and not complex, is
intended for use in reactor design purposes.
2.3. Preparation of homopolystyrene

2. Experimental
Following the recipe in Table 2, which is similar to Ta-
ble 1 without having NR latex, styrene monomer was
2.1. Materials
purged with nitrogen for 30 min prior to the subsequent
addition of isopropanol, E, and TEPA. Upon the addition
Fresh NR latex with a solid content of 60% was pur-
of CHPO, the mixture was continuously stirred for another
chased from Thailand Natural Rubber Research Institute.
15 min before being transferred to 30 mL bottles with caps
Styrene monomer (Merck, purity 99%) was puried by
on. Each bottle was then immersed in a water bath con-
washing several times with an aqueous solution of 15% so-
trolled at 40 C and collected at different reaction times.
dium hydroxide (NaOH). The redox initiator, cumene
The polymerization in each bottle was stopped by adding
hydroperoxide (CHPO; Fluka, purity 80%) and tetraethyl-
hydroquinone. The weight of each sample was recorded
ene pentamine (TEPA; Fluka, purity 85%), were used as
before and after drying in a vacuum oven at 60 C for
received. Potassium hydroxide (Fluka) for pH control, so-
24 h. The dried product is homopolystyrene. The monomer
dium dodecyl sulfate solution (E; Fluka, purity 90%) as
conversion was determined by gravimetric method.
an emulsier, and other chemicals were analytical grade
and used as received.

Table 2
2.2. Preparation of styreneNR graft copolymer Recipes for styrene emulsion polymerization.

Styrene (g) 100

Following the recipe in Table 1, identical to one found in
Deionized water (pph)a 1300
the literature [6], fresh NR latex in a 2-L spherical glass reac- Isopropanol (pph)a 7.60
tor was purged with nitrogen for 30 min prior to the subse- Emulsier (pph)a 3.70, 4.81, 5.54, 6.64
quent addition of isopropanol, E, TEPA, and styrene. The TEPA (pph)a 1.16, 1.63, 1.94, 2.35
mixture, maintained at pH 10 using KOH and at room tem- CHPO (pph)a 0.25, 0.35, 0.42, 0.48
Hydroquinone (pph)a 2.20
perature, was continuously stirred at a stirring speed of
Reaction temperature (C) 40
400 rpm for 45 min to allow rubber particles to swell with
a
styrene. Next, CHPO was delivered into the reactor, and pph = Parts per hundred.
 K. Songsing et al. / European Polymer Journal 49 (2013) 10071016
3. Results and discussion
3.1. Effect of molar ratio of CHPO to TEPA on styrene
conversion
The redox initiator system used in this work is com-
posed of CHPO as an oxidizing agent and TEPA as a reduc-
ing agent. To study the effect of the molar ratio of CHPO to
TEPA on the styrene conversion in the styreneNR graft
copolymerization, the molar ratio was varied from 1:8 to
1:0.5, while the total number of moles of CHPO and TEPA
and other ingredients were kept constant.
In Fig. 1, as the molar ratio is decreased, the percentage
of conversion signicantly increases and drops slightly
when the molar ratio reaches 1:8. Thus, rather than being
equimolar, the molar ratio of CHPO to TEPA suitable for
this styreneNR graft copolymerization is 1:4; this ratio
was then used throughout this work, i.e., in both graft
copolymerization and homopolymerization. This optimal
nonequimolar redox system, in which the mole of the
reducing agent is about four times as much as that of the
oxidizing agent, is also reported by a previous study [20],
in which CHPO and sodium formaldehyde sulfoxylate were
used as the oxidizing and reducing agents, respectively, in
the presence of ferrous sulfate hexahydrate and ethylene-
diaminetetraacetic acid monosodium salt for seeded emul-
sion polymerization of butyl acrylate. In addition, previous
evidence shows that TEPA is a water-soluble chain transfer
agent, used to control the molecular weight of polymer in
emulsion polymerization [21]. Consequently, some TEPA
can be lost by the transfer reaction to monomer or to poly-
mer near the aqueousorganic interface, and thus at the
interface less TEPA, as a reducing agent, reacts with CHPO,
which leads to a lower conversion. Increasing the TEPA
amount can thus raise the conversion in the current work.
The graft copolymerization recipe used herein is from
the literature [6], where, however, the styrene conversion
was not reported. Nonetheless, similar recipe (different ra-
tio of CHPO to TEPA was used) is applied for MMA/NR graft
copolymerization [10], of which the monomer conversion
80
60
Conversion (%)
40
20
0
1:0.5
Fig. 1. Comparison of conversion by variation of initiator molar ratio. Reaction time = 3 h, E0 = 1.12 pph ([E]0 = 13 mM), and I0 = 0.45 pph ([I]0 = 8.25 mM).
1009
at a reaction temperature of 50 C reaches 90%, higher than
what was reported in this current work. Thus, the low con-
version of styrene might be caused by using low reaction
temperature or, perhaps, the monomer itself.
The investigation of the effect of monomer type was
thus conducted in one of our other studies, similar to this
current work [22]. The results revealed that, for two sepa-
rate polymerizations of styrene and MMA using the same
redox initiator type (CHPOTEPA) and amounts under the
same reaction conditions, at the end of the styrene poly-
merization at 50 C the concentration of unreacted CHPO
decreased by a factor of 1.5, whereas at the end of the
MMA polymerization at 50 C the concentration of unre-
acted CHPO decreased by a factor of 4. These results were
in agreement with the higher maximum conversion found
for MMA polymerization than that for styrene polymeriza-
tion (80% and 35%, respectively). It should be noted that
the active radicals which can initiate these polymeriza-
tions are derived from CHPO molecules, not TEPA. Thus,
the measurement of unreacted CHPO, measured using the
iodometric method [23], is sufcient. The experimental re-
sults showing the higher concentration of unreacted CHPO
found at the end of the styrene polymerization and a lower
styrene conversion imply a lower efciency of CHPO
becoming active CHPO radicals for the styrene polymeriza-
tion than for the MMA polymerization. The possible expla-
nation may be related to the hydrophobic nature of CHPO
and styrene. As CHPO is known to be hydrophobic [24] and
styrene is more hydrophobic than MMA, CHPO can more
easily diffuse further into a styrene particle, leading to a
lower CHPO amount at the surface of the particle that
can react with TEPA to become active CHPO radicals.
3.2. Morphology of graftrubber particles
In grafting styrene onto NR particles, both graft copoly-
mer and homopolystyrene were formed. Only the mor-
phology of the former at different reaction times is
shown in Fig. 2, where the dark and bright domains repre-
sent NR and styrene components, respectively. In Fig. 2ac,
1:1 1:2 1:4 1:8
CHPO : TEPA molar ratio
1010 K. Songsing et al. / European Polymer Journal 49 (2013) 10071016

Fig. 2. Transmission electron micrographs of PS-graft-NR obtained at reaction time equal to (a) 32 min (b) 60 min and (c and d) 180 min. E0 = 1.55 pph
([E]0 = 18 mM), I0 = 0.45 pph (TEPA = 0.37 pph and CHPO = 0.08 pph, CHPO:TEPA molar ratio = 1:4, [I]0 = 8.25 mM).

the coreshell structure of a particle becomes obvious at
longer reaction times. In Fig. 2c, small bright domains
can be spotted in one of particles, and more bright domains
on particles can be discerned easily in Fig. 2d. The evi-
dence, thus, suggests the formation of styrene particles
on NR particles rather than a homogenous NR core. Further
examination of microtome sections may reveal additional
details of morphology [25].
In Fig. 2c, at 180 min (the conversion has already
reached a plateau for some time), obvious particle coagula-
tion occurs. This is due to the insufcient amount of emul-
sier adsorbed onto the particles. Such a coagulation is
very common in the emulsion polymerization, but it can
be prevented by decreasing the initiator concentration, as
suggested by Weerts et al. [26].
3.3. Rate of monomer consumption for the graft
copolymerization
To obtain the rate, the mechanism of the graft copoly-
merization between styrene monomer and NR should be
reviewed. In this work, all graft copolymerization at
various conditions occurs above the critical micellar con-
centration. Thus, polymerization occurs both in rubber
particles and in micelles containing styrene monomers.
That is, in addition to the formation of styreneNR graft
copolymer and styrene homopolymer in rubber particles,
styrene homopolymer resulting from the existence of
monomer-swollen micelles is generated. It is worth noting
that due to the fact that a monomer droplet has a larger
size than that of a micelle, leading to inefciency of the
droplet in competing for primary radicals, nucleation in
micelles is generally more dominant than that in droplets
[2729]. It is also noteworthy that primary CHPO and TEPA
radicals are produced only at the aqueousorganic inter-
face, where they encounter each other because hydropho-
bic CHPO stays in the organic phase, whereas hydrophilic
TEPA is in the aqueous phase [12,24,30,31]. Luo and Schork
illustrated that only primary CHPO radical is dominantly
responsible for the formation of both graft copolymer in
rubber particles and hompolymer in aqueous and organic
phases [32]. As a result, reactions in the graft copolymeri-
zation between styrene monomer and NR initiated by
CHPOTEPA initiator can be described as follows.
 K. Songsing et al. / European Polymer Journal 49 (2013) 10071016 1011

At the aqueousorganic interface, the redox reaction 3.3.3. Chain transfer reactions
between CHPO (denoted by ROOH) and TEPA (denoted by In a graftrubber particle:
R0 NH2) is shown in eq. (1) [12,31]. ktr
In a rubber particle containing polyisoprene and styrene M n M ! M n M  9
monomer, polyisoprene radicals are produced by primary
CHPO radicals via the abstraction of a-methylenic hydro- ktr
M n P ! M n P 10
gen atoms or the addition to the polyisoprene [24,30].
Additionally, styrene radicals are generated by primary ktr
CHPO radicals as the latter are added to the monomer P  Mn M ! P  M n M  11
[12]. The polyisoprene radicals then react with monomer
ktr
to form growing graft copolymer radicals, while the sty- P  Mn P ! P  Mn P 12
rene radicals react with monomer to form growing poly-
mer radicals. The growing chain radicals can transfer to In a homopolystyrene particle:
monomer or to polyisoprene to form monomeric or poly- ktr
M n M ! M n M  13
meric radicals, respectively, as well as terminated poly-
mers. The newly generated radicals can reinitiate (Assuming that all transfer reactions have the same rate
polymerization of monomer or graft copolymer. Further- constants, ktr).
more, for termination reactions terminated polymers are
mainly formed by combination [33]. 3.3.4. Termination reactions
Similarly, the reactions above can take place in a mono- In a graftrubber particle:
mer-swollen micelle. But only styrene radicals and grow-
kt
ing styrene polymer radicals are formed, a process which M n Mm ! M nm 14
eventually yields only homopolymer chains.
In consequence of aforementioned description, the kt
P  Mn P  Mm ! P  M nm  P 15
mechanism of styreneNR graft copolymerization using
CHPOTEPA redox initiator is summarized as follows: kt
P  Mn Mm ! P  Mnm 16
3.3.1. Initiation reactions In a homopolystyrene particle:
Decomposition of the redox initiator (in both a rubber
kt
particle and a micelle): M n Mm ! M nm 17
kd (Assuming that all termination reactions have the same
ROOH R0 NH2 ! RO R0 NH H2 O 1
rate constants, kt).
In a rubber particle: Let kd, ki, kp, ktr, and kt be rate constants for the decom-
ki1 position of the initiator, initiation, propagation, chain
RO M ! M  2 transfer, and termination reactions, respectively. P repre-
sents a polyisoprene chain. M n (or M m ), P, and P  M n rep-
ki2
RO P ! P 3 resent a growing homopolystyrene radical, an initiated
polyisoprene, and a growing graft copolymer radical with
ki3 polyisoprene as an endgroup (of all lengths) in the system,
P M ! P  M 4
respectively, with or without initiator end groups. Mn+m
In a micelle: and P  Mn+m  P (or P  Mn+m) symbolize a dead homo-
ki4
polystyrene chain and a dead graft copolymer (with differ-
RO M ! M  5 ent endgroups) chain.
According to the mechanism above and an assumption
that rate constants of the polymerization reinitiation of
3.3.2. Propagation reactions of homopolymer and graft
radicals generated from chain transfer reactions are close
copolymer
to those of propagation reactions (kp), the rate of graft
(Assuming all radicals have the same reactivity, repre-
copolymerization (Rgc) is equal to the consumption rate
sented by the rate constant kp).
of styrene monomer in homopolymer and graftrubber
In a graftrubber particle (i.e., the rubber particle in
particles [34],
which graft copolymerization between NR and polystyrene
occurs): Rgc kp Mh M h kp Mg P  M  g M  g 18
kp where kp is the propagation rate constant (independent of
M  M ! Mn 6
polymer length or of endgroup type), and [M]h and [M]g are
kp
monomer concentrations in homopolystyrene and graft
P  M M ! P  M n 7 rubber particles, respectively. [M]h, [P  M]g, and [M]g
are radical concentrations in homopolystyrene and graft
In a homopolystyrene particle:
rubber particles, respectively.
kp Based on SmithEwart case 2 kinetics, the number of
M  M ! Mn 8 free radicals per polymer particle is 0.5. Termination
1012 K. Songsing et al. / European Polymer Journal 49 (2013) 10071016
reactions occur rapidly once the second radical comes into
a particle, in which one radical already resides [29]. That is,
Eq. (18) is rewritten as
Nh Ng
Rgc kp Mh kp Mg
2NAV 2NAV
where Nh is the number of homopolystyrene particles per
unit volume and Ng is the number of graftrubber particles
per unit volume. NAV is Avogadros constant.
Smith and Ewart also showed that the number of poly-
mer particles evolved from micelles per unit volume (Nh) is
proportional to [I]0.4[E]0.6, where [I] and [E] are concentra-
tions of initiator and emulsier, respectively [28,29]. Like-
wise, Ng should be a function of [I] and Nr (Nr is the total
number of rubber particles in the system per unit volume).
As the current work uses different initiator type (as op-
posed to the thermal initiator), the general form of Eq.
(19) that is modied according to Smith and Ewart
[28,29] should be
Rgc kp Mh k1 Ix1 Ey kp Mg k2 Ix2 Nr
where k1, k2, x1, x2, and y are constant values.
Classical emulsion polymerization is divided into three
main intervals: Interval I (particle nucleation), Interval II
(particle growth), and Interval III (the continuous reduc-
tion in concentration of monomer in particles towards
zero, which is the end of the polymerization)
[26,27,32,3538]. The rate of polymerization increases
and becomes constant in the second interval, in which
large monomer droplets exist and continuously supply
monomer to all particles in the system, resulting in con-
stant [M]h and [M]g. Also, in this current work, Nr is xed.
Hence, Eq. (20) can be reduced to
0 00
Rgc kp Ix1 Ey kp Ix2
0 00
where kp kp Mh k1 and kp kp Mg k2 N r . Exponents (x1, x2,
0 00
and y) as well as kp and kp are determined by employing a
curve-tting technique and experimental data, as shown in
the next section.
60
50
Conversion (%)
40
30
20
10
0
0 20
Fig. 3. Conversion versus time prole of styrene/NR graft copolymerization. E0 = 1.55 pph ([E]0 = 18 mM) and I0 = 0.45 pph (TEPA = 0.37 pph and
CHPO = 0.08 pph, CHPO:TEPA molar ratio = 1:4, [I]0 = 8.25 mM).
Fig. 3 shows the percentage conversion varied with
time for styreneNR graft copolymerization, which also
represents the graft copolymerizations occurring at other
conditions. Additionally, the rapid increase in conversion
19 as the reaction proceeds and reaching a plateau around
100 min are discerned, as seen in the literature, when per-
forming styrene/MMA/NR graft copolymerization initiated
by CHPO and TEPA [39].
Fig. 3 shows that Interval I is very short, followed by
Interval II with constant polymerization rate and then
Interval III with the polymerization rate diminishing to
zero. The fastest rising portion of the curve (Interval II)
yields the initial rate of polymerization, Rgc0. Note that as
Rgc0 is the initial polymerization rate, those concentrations
of initiator and emulsier are initial concentrations as well,
denoted by subscript zero. The Rgc0 values at different [I]0
and [E]0 were employed to determine parameters in Eq.
(21), using LevenbergMarquardt curve-tting method. In
this current work, [I]0 denotes the total initial concentra-
tion of CHPO and TEPA. The result is thus shown in the fol-
20
lowing equation:
Rgc0 2:5  103 I1:03
0 E0:88
0 4:0  102 I0:91
0 22
Eq. (22) tted to the experimental results with coefcient
of correlation (R2) higher than 0.9 and with data points
randomly scattered around the regression line (Fig. 4a
b). Additionally, Fig. 5 displays that most data are clustered
around the line with slope of one, conrming the closeness
of calculated and experimental values and the good t of
Eq. (22) to experimental data.
Eq. (22) with the rst term on the right-hand side hav-
ing a much larger coefcient indicates that most of mono-
mer molecules are consumed in polymer particles, rather
21 than in graftrubber particles. Note that this result may
need verication by measuring the level of homopolysty-
rene produced. Moreover, it can be discerned that expo-
nents of initial initiator and emulsier concentrations in
the rst term on the right-hand side deviate from the
SmithEwart theory [29], which may suggest increases in
40 60 80 100 120 140 160 180
Reaction time (min)
 K. Songsing et al. / European Polymer Journal 49 (2013) 10071016 1013

(a) 1.0
calculated using eq.(22)
experimental
.8

Rgc0 (mol L-1 min-1)

.6

.4

.2
2
R = 0.91

0.0
.004 .006 .008 .010 .012 .014
-1
[I]0 (mol L )

1.00
(b)
calculated using eq.(22)
experimental

.75
Rgc0 (mol L-1 min -1)

.50

.25

2
R =0.92

0.00
.008 .010 .012 .014 .016 .018 .020
-1
[E]0 (mol L )

Fig. 4. Dependence of the rate of styrene/NR graft copolymerization on (a) initiator concentration [E0 = 1.12 pph ([E]0 = 13 mM) and CHPO:TEPA molar
ratio = 1:4] and (b) emulsier concentration [I0 = 0.45 pph (TEPA = 0.37 pph and CHPO = 0.08 pph, CHPO:TEPA molar ratio = 1:4, [I]0 = 8.25 mM)].

both initiators efciency and emulsiers efciency. Re-
sults in the following section (i.e., styrene polymerization)
obtained from experiments using the same ingredient
amount, but without NR, are shown to examine whether
the deviation from the classic theory is caused by the pres-
ence of NR.
3.4. Rate of styrene polymerization
The rate of homopolymerizationactually the rate of
propagation stepis constant in Interval II and determined
by measuring the rate of monomer consumption,
Rh kp Mh M  h
where kp is the propagation rate constant for homopoly-
merization, [M]h is the monomer concentration in homo-
polystyrene particles, and [M]h is the radical
concentration in homopolystyrene particles. Smith investi-
gated the kinetics of homopolystyrene using potassium
persulfate as a thermal initiator and found that the kinetics
follows SmithEwart case 2, in which the number of free
radicals per polymer particle is 0.5 [28,29]. That is,
M  h 2NNhAV , where Nh is the number of homopolystyrene
particles per unit volume, and Nh / [I]0.4[E]0.6 [28]. Hence,
this suggests that
Rh / Ia Eb 24
where a and b are constant values. [I] in Eq. (24) is the total
concentration of CHPO and TEPA.
In Fig. 6, the change in percentage conversion with time
for styrene polymerization is similar to that for graft copo-
lymerization in Fig. 3. The polymerizations at other condi-
23
tions also show the same rapid increase trend and reach
plateau levels around 100 min. The initial rate of polymer-
ization, Rh0, was obtained from the slope of the fastest ris-
ing portion of the curve (Interval II) and was measured as a
function of [I]0 and [E]0. For the determination of a, only
[I]0 was varied, and for the determination of b, only [E]0
was altered. Furthermore, tting Eq. (24) to experimental
1014 K. Songsing et al. / European Polymer Journal 49 (2013) 10071016

1.0

The calculated Rgc0 (mol L-1 min-1)

.8

.6

.4

.2

0.0
0.0 .2 .4 .6 .8 1.0

The experimental Rgc0 (mol L-1 min-1)

Fig. 5. Calculated Rgc0 values using Eq. (22) versus experimental Rgc0 values.

60

50
Conversion (%)

40

30

20

10

0
0 20 40 60 80 100 120 140 160 180
Reaction time (min)

Fig. 6. Conversion versus time prole of styrene homopolymerization. E0 = 6.64 pph ([E]0 = 13 mM) and I0 = 1.98 pph (TEPA = 1.63 pph and
CHPO = 0.35 pph, CHPO:TEPA molar ratio = 1:4, [I]0 = 8.25 mM).

data by using the combination of loglog plots and linear initiator efciency. Note that the reaction temperature of
regression was employed to determine exponents (a and the current work is 40 C, 10 C lower than that of Smith
b), which, in turn, imply effects of [I]0 and [E]0 on the initial [28]. The ability to work at a lower temperature is one of
polymerization rate. advantages of the CHPOTEPA redox initiator over other
The tting results are shown in Fig. 7a and b, and can be initiators.
summarized as Because exponents of initiator and emulsier concen-
trations are increased to approximately 1.0 and 0.9, respec-
Rh0 / I0:43
0 E0:61
0 25 tively, for graft copolymerization, as compared to the
2
R values for both ttings are greater than 0.99, indica- respective powers of 0.43 and 0.61 for homopolymeriza-
tive of strong linear relationships between ln(Rh0) and tion, this substantiates that the presence of NR causes
ln[I]0 and between ln(Rh0) and ln[E]0. Furthermore, the the deviation of effects of initiator and emulsier concen-
exponents of [I]0 and [E]0 in Eq. (25) agree well with the lit- trations from the classic theory. Additionally, at the same
erature [28]. As Smith [28] carried out the styrene poly- concentrations of initiator and emulsier, all measured
merization using an emulsion polymerization process Rgc0 values are higher than measured Rh0 values (see
with anionic surfactant and potassium persulfate initiator, Fig. 4a and b for graft copolymerization and Fig. 7a and b
similar exponents may imply that CHPOTEPA redox initi- for homopolymerization). This implies that NR molecules
ator and potassium persulfate initiator, although having promote the rate of monomer consumption; the addition
different dissociation mechanisms, have comparable of NR enhances the number of reaction loci in the system
 K. Songsing et al. / European Polymer Journal 49 (2013) 10071016 1015

-.7
(a)
-.8

ln (Rh0) (mol L-1 min-1)

-.9

-1.0

-1.1

-1.2 y = 0.4273x+0.9988
2
R = 0.9973

-1.3
-5.2 -5.0 -4.8 -4.6 -4.4
-1
ln [I]0 (mol L )

-.9
(b)
-1.0
ln (Rh0) (mol L-1 min-1)

-1.1

-1.2

-1.3

-1.4 y = 0.6055x+1.3779
2
R = 0.9922
-1.5
-4.6 -4.4 -4.2 -4.0
-1
ln [E]0 (mol L )

Fig. 7. Dependence of the rate of styrene polymerization on (a) initiator concentration [E0 = 6.64 pph ([E]0 = 13 mM) and CHPO:TEPA molar ratio = 1:4] and
(b) emulsier concentration. [I0 = 1.98 pph (TEPA = 1.63 pph and CHPO = 0.35 pph, CHPO:TEPA molar ratio = 1:4, [I]0 = 8.25 mM)].

and interfacial area for contacts between CHPO and TEPA
[18]. It should be noted that the enhancement of the poly-
merization rate due to the presence of polymer seeds has
been reported in literature [40].
4. Conclusion
To graft styrene onto natural rubber using emulsion
polymerization with CHPOTEPA redox initiator, the opti-
mal molar ratio of CHPO to TEPA was 1:4 and thus used
throughout this work. The additional amount of TEPA
probably compensates for the loss of TEPA in chain transfer
reactions. The mechanism covering reactions occurring in
both rubber particles and micelles, producing both graft
copolymer and homopolystyrene, was reviewed to develop
the rate of graft copolymerization in terms of initiator and
emulsier concentrations. Parameters in the mathematical
expression for the rate were determined by tting the
equation to experimental data. Graph visualization and
high R2 values conrmed the good t between predicted
and measured rates of graft copolymerization. The rate
expression implies that more monomer is consumed in
polymer particles than in rubber particles. In addition,
the dependences of the rate on initiator and emulsier
concentrations for the graft copolymerization are much
greater than those for the styrene polymerization, which
agrees well with the SmithEwart theory. This is contrib-
uted from the presence of NR particles, which act as reac-
tion loci.
Acknowledgments
We gratefully acknowledge nancial support from the
following in alphabetical order: Center of Advanced Stud-
ies in Industrial Technology, Faculty of Engineering,
Kasetsart University; Center of Excellence for Petroleum,
Petrochemicals and Advanced Materials, S&T Postgraduate
Education and Research Development Ofce (PERDO);
Kasetsart University Research and Development Institute
1016 K. Songsing et al. / European Polymer Journal 49 (2013) 10071016
(KURDI). We are also grateful to Dr. Ben Embley for proof-
reading our manuscript.
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