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Reaction kinetics of the catalytic esterication of acrylic acid

with propylene glycol


Mehmet R. Altokka *, Elif O

des
Department of Chemical Engineering, Anadolu University, 26470, Eskis ehir, Turkey
1. Introduction
Various acrylic esters are useful chemicals. Their excellent
clarity, toughness, color retention, UV stability and chemical
inertness make acrylic ester emulsion polymers prime paint
binders. Acrylics are widely used in all types of paint formulations.
Large volumes of acrylic emulsion polymers are used as binders for
berll and nonwoven fabrics, textile bonding or laminating,
ocking, back coating and pigment printing binders. These are also
used for leather nishing, textile and berll bonding and as
adhesives [1].
Among the other many acrylates, hydroxypropyl acrylates are
used in production of acrylate polymers [24] and as a co-
monomer in adhesives, elastomers [5], inks, radiation curable [6],
automotive top coating, nanocomposites materials [7], photo cure
resins and oil additives and as a viscosity reducer [8].
Hydroxypropyl acrylate contains both vinyl and hydroxyl
functionality. Vinyl allows copolymerization with a variety of
other vinyl monomers in aqueous and nonaqueous systems. Wide
co-monomer selection provides easy control of physical and
chemical properties such as glass transition temperature and
solution viscosity. On the other hand hydroxyl functionality of
hydroxypropyl acrylate provides the reaction readily with
oligomeric di- or polyisocyanates, anhydrides, or epoxides. The
resulting adducts carry pendant vinyl unsaturation making these
resins radiation curable by ultraviolet light or an electron beam[9].
Esterication of acrylic acid with alcohol has been performed
commercially by using homogeneous catalysts such as sulfuric
acid, hydrouoric acid and para-toluenesulfonic acid; but these are
toxic, corrosive and often hard to remove from the products. Thus
it is keenly desirable to develop newtypes of solid acid catalysts to
replace them, because the solid acid is less toxic and facilitates the
recovery and recycling of catalysts [10,11].
No study has been reported in the literature for the esterica-
tion of acrylic acid with propylene glycol. However, a number of
studies related to the catalytic esterication reactions of acrylic
acid with some other alcohols have been reported. Although the
catalytic activities of the various types of catalysts were compared
with each other, kinetic information has not been given in these
studies [1,1218].
Esterication reaction between acrylic acid and 2-ethylhexanol
was investigated in an isothermal semi-batch reactor by using
sulfuric acid as a homogeneous catalyst. The reaction kinetics was
found to be second order [14].
Esterication of acrylic acid with 1-butanol has been studied in
the presence of Cs
2.5
H
0.5
PW
12
O
40
, solid oxides and organic resins
as heterogeneous catalysts. In this solidliquid reaction system it
was found that Cs
2.5
H
0.5
PW
12
O
40
exhibited the highest catalytic
activity, in the unit of catalyst weight, among the solid oxide
catalysts, while the activity Cs
2.5
H
0.5
PW
12
O
40
was less than those
of organic resins such as Naon and Amberlyst-15 [16].
In the study of transesterication of cyclohexyl acrylate with
n-butanol and 2-ethylhexanol, it was found that while the acid
Applied Catalysis A: General 362 (2009) 115120
A R T I C L E I N F O
Article history:
Received 8 January 2009
Received in revised form 12 March 2009
Accepted 15 April 2009
Available online 23 April 2009
Keywords:
Esterication
Hydroxypropyl acrylate
Heterogeneous catalysis
Kinetic modeling
A B S T R A C T
The kinetics of esterication of acrylic acid with propylene glycol has been studied in the presence of
Amberlyst-15 as a heterogeneous catalyst. The reaction was realized in a batch reactor at different
temperatures and initial reactant mol ratios. The simultaneous dimerization/polymerization of acrylic
acid and products, in addition to the reversible esterication reaction, was proposed as the reaction
mechanism. Kinetic equations corresponding to the reaction mechanism have also been developed.
Temperature dependence of the reaction rates and activation energies was determined.
2009 Elsevier B.V. All rights reserved.
* Corresponding author. Tel.: +90 222 321 35 50/6505; fax: +90 222 323 95 01.
E-mail address: mraltiokka@anadolu.edu.tr (M.R. Altokka).
Contents lists available at ScienceDirect
Applied Catalysis A: General
j our nal homepage: www. el sevi er . com/ l ocat e/ apcat a
0926-860X/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2009.04.028
treated clay, Engelhard F-24, was an effective catalyst for the
transesterication reaction at moderate temperatures, tetrabutyl
titanates as catalyst increase cyclohexanol selectivity at higher
temperatures. It was also shown that transesterication reaction
follows LHHW mechanism in the presence of Engelhard F-24 [1].
In another study it has been reported that heteropoly acids,
such as phosphorous tungstic acid, show higher activities than the
conventional acids in the esterication of methacrylic acid with
tripropylene glycol [17].
The role of Mn and Fe as promoters of sulfated zirconia has been
studied in the reaction of acrylic acid esterication by 1-butene to
sec-butyl acrylate at 343 K. It was reported that Mn and Fe did not
improve the catalytic activity and selectivity to sec-butyl acrylate
compared with Amberlite resins or sulfuric acid but they strongly
resist deactivation [18].
In the present work, Amberlyst-15 and Amberlyst-36 and
cesium salt of phosphorous tungstic acid were used as the
heterogeneous catalysts for the esterication of acrylic acid with
propylene glycol. The best catalyst among them was to be
determined in point of activity and selectivity towards hydro-
xypropyl acrylate. Thereafter, the kinetic study of esterication
was to be studied at the present of the selected catalysts among the
catalysts tested.
2. Experimental
2.1. Materials
Acrylic acid (>99.5%) and propylene glycol (>99%) were
obtained from Acros. Toluene, as a solvent, was supplied by
SigmaAldrich. Properties of catalysts used in this study are given
in Table 1. The catalysts were dried at 80 8C for overnight prior to
the experiment. Phenothiazine used as polymerization inhibitor
was obtained from Fluka.
2.2. Equipments
The reactor consisted of a two-necked spherical Pyrex ask of
250 ml capacity tted with a spiral coil condenser and a sample
device. The temperature was controlled within 0.1 K by circulat-
ing water from a thermostat into the water jacket of the reactor. The
reaction mixture was magnetically stirred at about 600 rpm.
2.3. Experimental procedure
In a typical run, toluene as a solvent and one reactant were
placed in the reactor. A known amount of catalyst and inhibitor
was added and the reactor contents were mixed well. After a
steady value of desired temperature was attained, the second
reactant was added and this was taken as zero time for a run. One
milliliters of the liquid sample was withdrawn from the reactor at
regular intervals for analysis and immediately transferred to a
crucible in an ice bath in order to ensure that no further reaction
took place.
2.4. Analysis
The samples were analyzed with a gas chromatograph (HP 5890
Series II) equipped with a ame ionization detector (FID) and a
capillary column (TRB-FFAP). The column oven was held at 313 K
for 3 min, ramped at 10 K/min to 333 K held for 3 min, followed by
10 K/min ramp-up to 433 K, held for 4 min and then ramped at
10 K/min to 453 K, held for 2 min. The concentration of water in
the reaction mixture was measured by Karl Fischer titration
(Metrohm KF-784). After verifying that the measured water
content corresponds to the calculated values based on stoichio-
metric equation, the amount of water was determined from
stoichiometric mass balance equation.
3. Results and discussion
The effects of parameters, such as catalyst type and loading,
temperature and reactant mol ratio, on the reaction rate were
studied.
Swelling effect of the catalyst was neglected since preliminary
experiment showed that the swelling process reaches the
equilibrium in a few minutes that the reactions were realized in
the presence of the reasonably stable catalyst. Therefore, the
proposed model in this work comprises the effect of catalyst
swelling.
3.1. Catalyst selection
In the experiments, two types of ion exchange resins
(Amberlyst-15 and Amberlyst-36) as well as cesium salt of
phosphorous tungstic acid exhibiting self-inhibiting effect for
polymerization [16], have been tested as the heterogeneous
catalysts. Experiments were carried out at 353 K and reactant mol
ratio of 1/1 with the same amount of catalyst and inhibitor. Results
are given in Table 2. As seen from Table 2 that Amberlyst-36
accelerates the reaction rate most. But its product selectivity is
considerably lower than that of Amberlyst-15 at the same
conversion level of 0.45. On the other hand, although its selectivity
is very high (100%), the activity of cesium salt of phosphorous
tungstic acid is very low compared to that of the others and it
should also be noticed that its selectivity is given at very low
conversion of 0.04. It is believed that this high selectivity cannot be
sustained in entire range of conversion. Therefore Amberlyst-15
was chosen as a heterogeneous catalyst in this study.
Effect of inhibitor, phenothizine, loading was also studied in the
presence of 0.1, 0.3 and 0.5 (wt%) in the reaction mixture. The best
ratio was found to be 0.3 (wt%). This ratio was also proposed in
literature [1214].
3.2. Effect of catalyst loading
Experiments were carried out in the presence of 3.11, 5.06 and
8.46 wt% of Amberlyst-15 on dry basis keeping the other
parameters constant. At the conversion levels less than 10% the
initial reaction rate can be safely calculated by using Eq. (1):
r
A0

C
A0
X
A
t
(1)
Nomenclature
C concentration (mol/L)
X conversion
t time (min)
r reaction rate (mol/L min)
CsHPA cesium salt of phosphorous tungstic acid
T absolute temperature (K)
k reaction rate constant (L/mol min)
K equilibrium constant
E activation energy (kJ/mol)
Subscripts
A, P, T and W acrylic acid, propylene glycol, hydroxypropyl
acrylate and water, respectively
M.R. Altokka, E. O

des / Applied Catalysis A: General 362 (2009) 115120 116


A plot of the reaction rate, calculated from Eq. (1), vs. catalyst
loading is given in Fig. 1. As seen in Fig. 1, the reaction rate
increases linearly, as expected, with catalyst loading since the
active surface area is proportional to the amount of catalyst.
Intersection of the line with ordinate will give the uncatalyzed
reaction rate at given parameters. The mathematical expression
relating the initial reaction rate to the catalyst loading can be
derived from Fig. 1 as follows:
r
A0
0:0002 0:0004%wt mol=L:min (2)
where (wt%) is the weight percent of the catalyst on dry basis in the
reaction mixture. It should also be kept in mind that Eq. (2) is valid
only at the given parameters of 0.3 (wt%) inhibitor, 1/1 reactant
mol ratio and 353 K at which the experiments were performed.
However, it does not alter the conclusion that the general reaction
rate increases linearly with the catalyst loading.
3.3. Effect of initial concentration
Initial reaction rate was determined by altering the concentra-
tion of the component under investigation while keeping those of
the others constant. The results are shown in Figs. 25. The
ordinate values of these gures were obtained fromEq. (1) by using
the experimental data. It is evident from these gures that all
reactants and products are adsorbed on the catalyst since the
initial reaction rate is becoming nearly independent of the
concentrations as their corresponding values increase [19].
However, the initial reaction rate, as seen in Figs. 2 and 4, is not
completely independent of the concentrations of acrylic acid and
product. This is attributed to their dimerization/polymerization
reaction.
3.4. Kinetic modeling
As seen in Figs. 25, reaction rate is highly temperature
sensitive. It is almost doubling in every temperature rising of 10 K.
Therefore, it is reasonable to accept that the overall reaction is
controlled by the surface reaction since internal and external
Table 1
Properties of catalysts reported by manufacturer.
Amberlyst-15 Amberlyst-36 Cs
2.5
H
0.5
PW
12
O
40
Manufacturer Rohm & Haas Co. Rohm & Haas Co. Nippon Organic Colour
& Chemical Company
Matrix Styrene-divinylbenzene
(macroreticular)
Styrene-divinylbenzene
(macroreticular)

Standard ionic form H


+
H
+

Surface area (m
2
/g) 50
a
33 116
a
% Moisture 48 55
Particle size (mm) 0.230.6 0.60.85
Cation exchange capacity (mmol/g) 4.7 5.4 0.15
a
Maximum operating temperature (K) 393 423
a
Ref. [16].
Table 2
Effect of catalyst type on the reaction rate and product selectivity at 353 K and in the presence of 0.3 (wt%) inhibitor.
Catalyst Catalyst
loading (wt%)
Conversion
time (min)
Initial
concentration (M)
Conversion r
Aav

C
A0
X
A
t
(mol/L min 10
3
)
Selectivity
C
A0
C
P0
CsHPA
a
4.73 180 3.3 2.9 0.04 0.736 1.00
Amb36 5.57 240 2.7 2.2 0.45 5.047 0.494
Amb15 5.54 420 2.8 2.3 0.45 3.003 0.736
a
Inhibitor is not used since it has self-inhibiting effect [16].
Fig. 1. Effect of catalyst loading on the reaction rate at 353 K, 0.3 (wt%) inhibitor, and
1/1 reactant mol ratio.
Fig. 2. Effect of acrylic acid concentration on the initial reaction rate (C
P0
= 0.83 mol/
L, 5 (wt%) catalyst on dry basis, and 0.3 (wt%) inhibitor).
M.R. Altokka, E. O

des / Applied Catalysis A: General 362 (2009) 115120 117


diffusions, as the physical steps, are not strongly temperature
dependent. This conclusion was further conrmed by Eq. (2),
verifying the Madon Boudart test stating that reaction rate is
proportional to the catalyst loading [20].
It is also reported that the inuence of external and internal
diffusions can be neglected for most of the reactions catalyzed by
the Amberlyst series resins [2129].
As concluded, from Figs. 25, that both reactants and products
are adsorbed on the catalyst surface. Under these assumptions the
general reaction stoichiometry and corresponding reaction rate
expression, in the form of LangmuirHinshelwoodHougen
Watson model, can be written as:
CH
2
CHCOOH
A
CH
3
CHOHCH
2
OH
P
, CH
2
CHCOOC
3
H
6
OH
T
H
2
O
W
(3)
r
00
A

kC
A
C
P
C
T
C
W
=K
1 K
A
C
A
K
P
C
P
K
T
C
T
K
W
C
W
K
U
C
U

2
(4)
respectively, where U is solvent.
Eq. (4) involves seven arbitrary constants that must be
evaluated. This makes it rather impractical. For this reason, some
simplied rate expressions, tting experimental data, were
proposed in literature [30]. Furthermore, Eq. (3) will never be
held due to simultaneous polymerization of acrylic acid and
products.
Taking into account the general estericationreaction as well as
polymerization of acrylic acid and products, the overall reaction
mechanism is proposed to be:
A P,
k
1
k
2
T W; esterificationreaction (5a)
2A)
k
3
dimer (5b)
2T)
k
4
dimer (5c)
Some of the dimer molecules formed here may transform into
polymer.
Assuming that each reaction step is elementary, the corre-
sponding rate expression can be written as follows:
dC
A
dt
k
1
C
A
C
P
k
2
C
T
C
W
k
3
C
2
A
(6a)
dC
P
dt
k
1
C
A
C
P
k
2
C
T
C
W
(6b)
dC
T
dt
k
1
C
A
C
P
k
2
C
T
C
W
k
4
C
2
T
(6c)
dC
W
dt
k
1
C
A
C
P
k
2
C
T
C
W
(6d)
In Eqs. (6s), concentrations were used instead of activities since
activity can be dened as:
a
i
g
i
c
i
(7)
The coefcient g
i
can readily be combined with the reaction rate
constants in Eqs. (6s). Furthermore, to use concentrations instead
of activities is more practical.
The reaction rate constants, k
1
, k
2
, k
3
and k
4
, in Eqs. (6s) were
determined by applying nonlinear regression analysis in MATLAB
7.0 program to the experimental data for each temperature.
Results together with their condence limits are given in Table 3.
3.5. Effect of temperature
Applying the Arrhenius equation to the values in Table 3, the
temperature dependency of the constants as well as their
corresponding activation energies was found to be:
k
1
exp22:17 9667=T L=mol min; DE 80:37kJ=mol (8a)
Fig. 3. Effect of propylene glycol concentration on the initial reaction rate
(C
A0
= 0.96 mol/L, 5 (wt%) catalyst on dry basis, and 0.3 (wt%) inhibitor).
Fig. 4. Effect of hydroxypropyl acrylate concentration on the initial reaction rate
(C
A0
= 1.06 mol/L, C
P0
= 0.84 mol/L, 5 (wt%) catalyst on dry basis, and 0.3 (wt%)
inhibitor).
Fig. 5. Effect of water concentration on the initial reaction rate (C
A0
= 0.96 mol/L,
C
P0
= 0.71 mol/L, 5 (wt%) catalyst on dry basis, and 0.3 (wt%) inhibitor).
M.R. Altokka, E. O

des / Applied Catalysis A: General 362 (2009) 115120 118


k
2
exp13:83 7797=T L=mol min; DE 64:82kJ=mol (8b)
k
3
exp62:63 24; 710=T L=mol min; DE
205:44kJ=mol (8c)
k
4
exp30:56 12; 340=T L=mol min; DE
102:59kJ=mol (8d)
where T is absolute temperature in K.
The equilibrium constant, depending on temperature, for
reaction (5a), can also be calculated from the values of k
1
and k
2
given in Eqs. (8a) and (8b) respectively, as follows:
K
k
1
k
2
exp1870=T 8:33 (9)
The heat of reaction, assuming independent of temperature
ranging from 333 to 358 K, calculated to be
DH 1:870 8:314 15:55kJ=mol (10)
This value is in good agreement with the literature value of
15.5 kJ/mol calculated by the method described in DIPPR 801 [31].
3.6. Comparison of model and experimental data
Using the numerical values of the reaction rate constants given
in Eqs. (8s), Eqs. (6s) was solved simultaneously by applying
RungeKutta method for the chosen temperature. Thus concen-
trationtime curves based on the model were obtained under
given reaction conditions. These curves, together with the
experimental data, are shown in Figs. 68.
As seen in Figs. 68, there is a reasonably good agreement
between calculated curves and experimental points.
4. Conclusions
The kinetics of esterication of acrylic acid with propylene
glycol has been studied batchwise in the presence of Amberlyst-15
as heterogeneous catalyst. Phenothiazine (0.3 (wt%)) was also used
as inhibitor to reduce the polymerization of acrylic acid and
product. Taking into account the general esterication reaction as
well as polymerization of acrylic acid and products, the overall
reaction mechanism can be given by Eqs. (5s). Four rate constants
in Eqs. (6s) were also determined from the experimental data
applying MATLAB 7.0 program. Variations of these constants with
temperature are presented in Eqs. (8s). It was also concluded that
the selectivity of hydroxypropyl acrylate is signicantly low at
high conversion levels of acrylic acid. Therefore, to work at low
Table 3
The average values of rate constant with 95% condence interval at different temperatures (5 (wt%) catalyst on dry basis, and 0.3 (wt%) inhibitor).
T (K) k
1
(10
4
L/mol min) k
2
(10
4
L/mol min) k
3
(10
4
L/mol min) k
4
(10
4
L/mol min)
333 11.21 0.81 0.74 0.56 0.09 0.015 14.95 3.09
348 30.46 3.13 1.60 1.08 2.60 0.92 78.99 5.33
358 88.84 8.13 3.94 1.42 15.48 3.08 196.48 26.16
Fig. 7. Experimental points and calculated curve from Eqs. (6s) and (8s) (T = 348 K,
reactant mol ratio; 1/1, 5 (wt%) catalyst on dry basis, and 0.3 (wt%) inhibitor).
Fig. 6. Experimental points and calculated curve from Eqs. (6s) and (8s) (T = 333 K,
reactant mol ratio; 1/1, 5 (wt%) catalyst on dry basis, and 0.3 (wt%) inhibitor).
Fig. 8. Experimental points and calculated curve from Eqs. (6s) and (8s) (T = 358 K,
reactant mol ratio; 1/1, 5 (wt%) catalyst on dry basis, and 0.3 (wt%) inhibitor).
M.R. Altokka, E. O

des / Applied Catalysis A: General 362 (2009) 115120 119


conversion with a proper recycle of unreacted stream, after
product separation, is recommended in industrial usage.
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