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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


graft copolymer of the vinyl monomer and NR being able
Thailand is ranked as the fourth largest producer of nat- to reduce interfacial energy between the polymer and the
ural rubber (NR) in the world, and thus the Thai Govern- rubber phases and the domain sizes of those phases [3].
ment promotes rubbers usage in terms of making higher Graft copolymerization between rubber and vinyl
value-added products and expanding its range of applica- monomer is usually conducted using free-radical emulsion
tion [1]. One way to expanding rubbers usage is to im- polymerization, in which an initiator utilized in the poly-
prove its mechanical properties, which can be done by merization is either a redox initiator or thermal initiator
grafting vinyl monomer with better mechanical properties [49]. However, since most redox initiators are insensitive
onto NR [2]. Examples of vinyl monomers frequently used to oxygen and can work well at high pH, they are more
for grafting onto NR are methyl methacrylate (MMA) and suitable for polymerizations involving NR latex with
styrene. In addition to the inclusion of vinyl polymer with ammonia added for preservation purposes [10]. In addi-
better mechanical properties in NR matrix, the improved 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].
Corresponding author. Address: Center of Excellence for Petroleum, A redox initiator is composed of two components: a
Petrochemicals and Advanced Materials, Department of Chemical Engi-
hydrophobic oxidizing agent and a hydrophilic reducing
neering, Faculty of Engineering, Kasetsart University, Bangkok, Thailand.
Tel.: +66 2579 2083; fax: +66 2561 4621. agent, such as benzyoyl peroxideN,N0 -dimethylaniline,
E-mail addresses: g51650109@ku.ac.th (K. Songsing), fengttv@ku.ac.th cumene hydroperoxide (CHPO)tetraethylene pentamine
(T. Vatanatham), fengnyh@ku.ac.th (N. Hansupalak). (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 1009

3. Results and discussion at a reaction temperature of 50 C reaches 90%, higher than


what was reported in this current work. Thus, the low con-
3.1. Effect of molar ratio of CHPO to TEPA on styrene version of styrene might be caused by using low reaction
conversion temperature or, perhaps, the monomer itself.
The investigation of the effect of monomer type was
The redox initiator system used in this work is com- thus conducted in one of our other studies, similar to this
posed of CHPO as an oxidizing agent and TEPA as a reduc- current work [22]. The results revealed that, for two sepa-
ing agent. To study the effect of the molar ratio of CHPO to rate polymerizations of styrene and MMA using the same
TEPA on the styrene conversion in the styreneNR graft redox initiator type (CHPOTEPA) and amounts under the
copolymerization, the molar ratio was varied from 1:8 to same reaction conditions, at the end of the styrene poly-
1:0.5, while the total number of moles of CHPO and TEPA merization at 50 C the concentration of unreacted CHPO
and other ingredients were kept constant. decreased by a factor of 1.5, whereas at the end of the
In Fig. 1, as the molar ratio is decreased, the percentage MMA polymerization at 50 C the concentration of unre-
of conversion signicantly increases and drops slightly acted CHPO decreased by a factor of 4. These results were
when the molar ratio reaches 1:8. Thus, rather than being in agreement with the higher maximum conversion found
equimolar, the molar ratio of CHPO to TEPA suitable for for MMA polymerization than that for styrene polymeriza-
this styreneNR graft copolymerization is 1:4; this ratio tion (80% and 35%, respectively). It should be noted that
was then used throughout this work, i.e., in both graft the active radicals which can initiate these polymeriza-
copolymerization and homopolymerization. This optimal tions are derived from CHPO molecules, not TEPA. Thus,
nonequimolar redox system, in which the mole of the the measurement of unreacted CHPO, measured using the
reducing agent is about four times as much as that of the iodometric method [23], is sufcient. The experimental re-
oxidizing agent, is also reported by a previous study [20], sults showing the higher concentration of unreacted CHPO
in which CHPO and sodium formaldehyde sulfoxylate were found at the end of the styrene polymerization and a lower
used as the oxidizing and reducing agents, respectively, in styrene conversion imply a lower efciency of CHPO
the presence of ferrous sulfate hexahydrate and ethylene- becoming active CHPO radicals for the styrene polymeriza-
diaminetetraacetic acid monosodium salt for seeded emul- tion than for the MMA polymerization. The possible expla-
sion polymerization of butyl acrylate. In addition, previous nation may be related to the hydrophobic nature of CHPO
evidence shows that TEPA is a water-soluble chain transfer and styrene. As CHPO is known to be hydrophobic [24] and
agent, used to control the molecular weight of polymer in styrene is more hydrophobic than MMA, CHPO can more
emulsion polymerization [21]. Consequently, some TEPA easily diffuse further into a styrene particle, leading to a
can be lost by the transfer reaction to monomer or to poly- lower CHPO amount at the surface of the particle that
mer near the aqueousorganic interface, and thus at the can react with TEPA to become active CHPO radicals.
interface less TEPA, as a reducing agent, reacts with CHPO,
which leads to a lower conversion. Increasing the TEPA 3.2. Morphology of graftrubber particles
amount can thus raise the conversion in the current work.
The graft copolymerization recipe used herein is from In grafting styrene onto NR particles, both graft copoly-
the literature [6], where, however, the styrene conversion mer and homopolystyrene were formed. Only the mor-
was not reported. Nonetheless, similar recipe (different ra- phology of the former at different reaction times is
tio of CHPO to TEPA was used) is applied for MMA/NR graft shown in Fig. 2, where the dark and bright domains repre-
copolymerization [10], of which the monomer conversion sent NR and styrene components, respectively. In Fig. 2ac,

80

60
Conversion (%)

40

20

0
1:0.5 1:1 1:2 1:4 1:8
CHPO : TEPA molar ratio

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).
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 various conditions occurs above the critical micellar con-
longer reaction times. In Fig. 2c, small bright domains centration. Thus, polymerization occurs both in rubber
can be spotted in one of particles, and more bright domains particles and in micelles containing styrene monomers.
on particles can be discerned easily in Fig. 2d. The evi- That is, in addition to the formation of styreneNR graft
dence, thus, suggests the formation of styrene particles copolymer and styrene homopolymer in rubber particles,
on NR particles rather than a homogenous NR core. Further styrene homopolymer resulting from the existence of
examination of microtome sections may reveal additional monomer-swollen micelles is generated. It is worth noting
details of morphology [25]. that due to the fact that a monomer droplet has a larger
In Fig. 2c, at 180 min (the conversion has already size than that of a micelle, leading to inefciency of the
reached a plateau for some time), obvious particle coagula- droplet in competing for primary radicals, nucleation in
tion occurs. This is due to the insufcient amount of emul- micelles is generally more dominant than that in droplets
sier adsorbed onto the particles. Such a coagulation is [2729]. It is also noteworthy that primary CHPO and TEPA
very common in the emulsion polymerization, but it can radicals are produced only at the aqueousorganic inter-
be prevented by decreasing the initiator concentration, as face, where they encounter each other because hydropho-
suggested by Weerts et al. [26]. bic CHPO stays in the organic phase, whereas hydrophilic
TEPA is in the aqueous phase [12,24,30,31]. Luo and Schork
3.3. Rate of monomer consumption for the graft illustrated that only primary CHPO radical is dominantly
copolymerization responsible for the formation of both graft copolymer in
rubber particles and hompolymer in aqueous and organic
To obtain the rate, the mechanism of the graft copoly- phases [32]. As a result, reactions in the graft copolymeri-
merization between styrene monomer and NR should be zation between styrene monomer and NR initiated by
reviewed. In this work, all graft copolymerization at 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 Fig. 3 shows the percentage conversion varied with
a particle, in which one radical already resides [29]. That is, time for styreneNR graft copolymerization, which also
Eq. (18) is rewritten as represents the graft copolymerizations occurring at other
conditions. Additionally, the rapid increase in conversion
Nh Ng
Rgc kp Mh kp Mg 19 as the reaction proceeds and reaching a plateau around
2NAV 2NAV
100 min are discerned, as seen in the literature, when per-
where Nh is the number of homopolystyrene particles per forming styrene/MMA/NR graft copolymerization initiated
unit volume and Ng is the number of graftrubber particles by CHPO and TEPA [39].
per unit volume. NAV is Avogadros constant. Fig. 3 shows that Interval I is very short, followed by
Smith and Ewart also showed that the number of poly- Interval II with constant polymerization rate and then
mer particles evolved from micelles per unit volume (Nh) is Interval III with the polymerization rate diminishing to
proportional to [I]0.4[E]0.6, where [I] and [E] are concentra- zero. The fastest rising portion of the curve (Interval II)
tions of initiator and emulsier, respectively [28,29]. Like- yields the initial rate of polymerization, Rgc0. Note that as
wise, Ng should be a function of [I] and Nr (Nr is the total Rgc0 is the initial polymerization rate, those concentrations
number of rubber particles in the system per unit volume). of initiator and emulsier are initial concentrations as well,
As the current work uses different initiator type (as op- denoted by subscript zero. The Rgc0 values at different [I]0
posed to the thermal initiator), the general form of Eq. and [E]0 were employed to determine parameters in Eq.
(19) that is modied according to Smith and Ewart (21), using LevenbergMarquardt curve-tting method. In
[28,29] should be this current work, [I]0 denotes the total initial concentra-
tion of CHPO and TEPA. The result is thus shown in the fol-
Rgc kp Mh k1 Ix1 Ey kp Mg k2 Ix2 Nr 20
lowing equation:
where k1, k2, x1, x2, and y are constant values.
Rgc0 2:5  103 I1:03
0 E0:88
0 4:0  102 I0:91
0 22
Classical emulsion polymerization is divided into three
main intervals: Interval I (particle nucleation), Interval II Eq. (22) tted to the experimental results with coefcient
(particle growth), and Interval III (the continuous reduc- of correlation (R2) higher than 0.9 and with data points
tion in concentration of monomer in particles towards randomly scattered around the regression line (Fig. 4a
zero, which is the end of the polymerization) b). Additionally, Fig. 5 displays that most data are clustered
[26,27,32,3538]. The rate of polymerization increases around the line with slope of one, conrming the closeness
and becomes constant in the second interval, in which of calculated and experimental values and the good t of
large monomer droplets exist and continuously supply Eq. (22) to experimental data.
monomer to all particles in the system, resulting in con- Eq. (22) with the rst term on the right-hand side hav-
stant [M]h and [M]g. Also, in this current work, Nr is xed. ing a much larger coefcient indicates that most of mono-
Hence, Eq. (20) can be reduced to mer molecules are consumed in polymer particles, rather
0 00
Rgc kp Ix1 Ey kp Ix2 21 than in graftrubber particles. Note that this result may
need verication by measuring the level of homopolysty-
0 00
where kp kp Mh k1 and kp kp Mg k2 N r . Exponents (x1, x2, rene produced. Moreover, it can be discerned that expo-
0 00
and y) as well as kp and kp are determined by employing a nents of initial initiator and emulsier concentrations in
curve-tting technique and experimental data, as shown in the rst term on the right-hand side deviate from the
the next section. SmithEwart theory [29], which may suggest increases in

60

50
Conversion (%)

40

30

20

10

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

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).
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- follows SmithEwart case 2, in which the number of free
sults in the following section (i.e., styrene polymerization) radicals per polymer particle is 0.5 [28,29]. That is,
obtained from experiments using the same ingredient M  h 2NNhAV , where Nh is the number of homopolystyrene
amount, but without NR, are shown to examine whether particles per unit volume, and Nh / [I]0.4[E]0.6 [28]. Hence,
the deviation from the classic theory is caused by the pres- this suggests that
ence of NR.
Rh / Ia Eb 24
3.4. Rate of styrene polymerization
where a and b are constant values. [I] in Eq. (24) is the total
The rate of homopolymerizationactually the rate of concentration of CHPO and TEPA.
propagation stepis constant in Interval II and determined In Fig. 6, the change in percentage conversion with time
by measuring the rate of monomer consumption, for styrene polymerization is similar to that for graft copo-
lymerization in Fig. 3. The polymerizations at other condi-
Rh kp Mh M  h 23
tions also show the same rapid increase trend and reach
where kp is the propagation rate constant for homopoly- plateau levels around 100 min. The initial rate of polymer-
merization, [M]h is the monomer concentration in homo- ization, Rh0, was obtained from the slope of the fastest ris-
polystyrene particles, and [M]h is the radical ing portion of the curve (Interval II) and was measured as a
concentration in homopolystyrene particles. Smith investi- function of [I]0 and [E]0. For the determination of a, only
gated the kinetics of homopolystyrene using potassium [I]0 was varied, and for the determination of b, only [E]0
persulfate as a thermal initiator and found that the kinetics 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 and measured rates of graft copolymerization. The rate
[18]. It should be noted that the enhancement of the poly- expression implies that more monomer is consumed in
merization rate due to the presence of polymer seeds has polymer particles than in rubber particles. In addition,
been reported in literature [40]. the dependences of the rate on initiator and emulsier
concentrations for the graft copolymerization are much
4. Conclusion greater than those for the styrene polymerization, which
agrees well with the SmithEwart theory. This is contrib-
To graft styrene onto natural rubber using emulsion uted from the presence of NR particles, which act as reac-
polymerization with CHPOTEPA redox initiator, the opti- tion loci.
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 Acknowledgments
reactions. The mechanism covering reactions occurring in
both rubber particles and micelles, producing both graft We gratefully acknowledge nancial support from the
copolymer and homopolystyrene, was reviewed to develop following in alphabetical order: Center of Advanced Stud-
the rate of graft copolymerization in terms of initiator and ies in Industrial Technology, Faculty of Engineering,
emulsier concentrations. Parameters in the mathematical Kasetsart University; Center of Excellence for Petroleum,
expression for the rate were determined by tting the Petrochemicals and Advanced Materials, S&T Postgraduate
equation to experimental data. Graph visualization and Education and Research Development Ofce (PERDO);
high R2 values conrmed the good t between predicted 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- [19] Suppaibulsuk B, Rempel GL, Prasassarakich P. Polym Adv Technol
2011: doi: 10.1002/pat.2069.
reading our manuscript.
[20] Liu Z-g, Han Y, Zhou C, Zhang M-y, Li W-m, Zhang H-x, et al. Ind Eng
Chem Res 2010;49(16):7152.
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