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1 s2.0 S1385894715011377 Main
1 s2.0 S1385894715011377 Main
1 s2.0 S1385894715011377 Main
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
Continuous free-radical
a r t i c l e
i n f o
Article history:
Received 24 March 2015
Received in revised form 9 July 2015
Accepted 14 August 2015
Available online 22 August 2015
Keywords:
Poly acrylic acid
Microreactor
Kinetics
Free radical polymerization
a b s t r a c t
A microreactor platform with easily assembled reaction tubes is developed to study the kinetics of acrylic
acid polymerization in aqueous solutions. In this platform, two micromixers are used to start and terminate the polymerization reaction, and several coiled reaction tubes embedded in water baths control the
residence time. Operated at a total flow rate greater than 40 mL/min, the reaction is independent of the
monomer and initiator mixing. Experimental data showed that the orders of acrylic acid and potassium
persulfate were 1.5 and 0.5, respectively, with an activation energy of 67.4 kJ/mol, which is in accord with
the classical kinetic mode reported in the literature. The molecular weight of polyacrylic acid
(1.03 1051.76 105) also indicated that the microreactor platform works well with macromolecules.
Therefore, this technique will expand the viable methods applicable for kinetic studies.
2015 Elsevier B.V. All rights reserved.
1. Introduction
The application of microreactors in chemistry and chemical
engineering has garnered significant popularity over the last
15 years [1,2], since microreactors are superior to traditional reactors in many aspects. Characterized with a high surface-to-volume
ratio and short mass transfer distance, microreactors enable efficient heat exchange and reactant mixing [3,4], where rapid and
strongly exothermic reactions can be conducted isothermally [5].
The ability of microreactors to ensure the safety of dangerous
Corresponding author.
http://dx.doi.org/10.1016/j.cej.2015.08.055
1385-8947/ 2015 Elsevier B.V. All rights reserved.
chemical processes has also been exploited [6,7]. Free radical polymerization is a reaction with a high reaction enthalpy (e.g.,
DH = 66.9 kJ/mol for the polymerization of acrylic acid) [8] and
ultra-fast chain propagation rate [9]. Generally, most free radical
polymerizations are carried out in batch reactors, which often
gives products with broad molecular weight distributions if living
radical control methods are not used, such as atom transfer radical
polymerization (ATRP), reversible additionfragmentation chain
transfer polymerization (RAFT), and nitroxide mediated living radical polymerizations (NMP) [2]. The poor temperature control and
bad mixing performance in batch reactors has been sufficiently
demonstrated; thus, it is promising to use more efficient reactors
for polymerization reactions [10,11].
234
where (AA)n denotes the units of repeated AA. In the chain termination step, the free radicals combine with each other, forming dead
polymers.
For the free radical polymerization of AA, the overall polymerization rate can be expressed as
Rp
dAA
k AAn1 KBSn2
dt
where [AA] is the concentration of acrylic acid and [KBS] is the concentration of K2S2O8. The purpose of this work was to determine
kinetic parameters k, n1, and n2 using a microreactor platform.
3. Method and experimental setup
3.1. Microreactor system
In kinetics measurements, it is necessary to change reaction
time. Adjustment of the flow rate of the reactant solutions in a single tube length helps change the residence time, but it will also
affect the mixing performance in micromixers [33,34]. To eliminate the effect of flow rate variation on reactant mixing, the reaction time should be adjusted using tubes of different lengths. A
new microreactor platform facilitating tube length variation with
selective switch-on valves was developed in this study, and a schematic is shown in Fig. 1. The microreactor platform consists of 5
individual parts in water baths, including a mixing system used
to pre-heat and mix the monomer and initiator solutions in water
bath 1, two tubular systems used to adjust the reaction time in
water baths 2 and 3, an additional tubular system to extend the
reaction time in water bath 4, and a quenching system used to terminate the reaction in water bath 5.
In the mixing system, a T-junction micromixer (316-L stainless
steel) with three 1 mm diameter holes is used to mix the monomer
and initiator solutions. The micromixer is connected to the tubes to
pre-heat the reactants and implement the polymerization reaction
with 1/16 in. outer diameter capillaries, whose inner diameters (dc)
are also 1 mm (Fig. 1). The distance from the T-junction to the end
of the 1/16 in. capillary is 4.55.5 cm. Although this is negligible
compared to the length of the subsequent reaction tubes, it is sufficient for the mixing of the aqueous solutions, according to our
previous conclusions on the mixing performances of this type of
micromixer [33,34]. The temperature of the reactant solutions is
controlled by the pre-heating tubes (2 mm inner diameter and
3 m length) in water bath 1 from 80 to 95 C. The quenching system has a similar structure as the mixing system (Fig. 1), which
contains a 1 mm inner diameter micromixer and a pre-cooling
235
Table 1
Tubes volumes in the microreactor platform.*
Tube volumes from the first to the second T-junction (mL)
V1
V2
V3
V4
V5
V6
V7
6.06
V8
12.1
V9
18.4
V10
24.7
V11
30.9
V12
40.8
V13
50.6
V14
60.3
69.7
79.1
88.5
98.0
110.5
123.1
The volumes were calibrated by feeding water into the microreactor platform and then measuring the water volume, which was pressed out by N2 under each valve
condition.
236
where [Br2] and VBr2 are the concentration and volume of Br2; [Na2S2O3] is the concentration of Na2S2O3; Vexperiment and Vblank are the
volumes of the Na2S2O3 titrating samples and blank solution; Vsamples is the volume of the samples collected from the microreactor
platform, and QAA, QKBS, and QCW are the flow rates of AA, K2S2O8
solution, and cold water. According to the measured AA concentrations, the AA conversion can be expressed as
AAQ AA Q KBS
100%
X 1
AA0 Q AA
AA
where [AA]0 is the acrylic acid concentration in the original solution. The molecular weight of the PAA product was analyzed by
GPC. Ultrapure water was used as the eluent at a flow rate of
1 mL/min. The column temperature was 40 C. Standard PAA samples with average molecular weights (Mn) from 103 to 106 were
used for the calibration.
Fig. 2. Conversions of acrylic acid with varied residence times and different total flow
rates. The experiments were carried out at [AA]0 = 0.7 mol/L, [KBS]0 = 0.056 mol/L,
QAA:QKBS = 3:1, T = 95 C, and QCW = 10 mL/min (cold water for quenching).
237
Fig. 3. (a) Conversions of acyclic acid with various residence times at different
initial acyclic acid concentrations; (b) the fitting of log Rp with log[AA]. Other
experimental details are [KBS]0 = 0.056 mol/L, QAA = 30 mL/min, QKBS = 10 mL/min,
T = 95 C, and QCW = 10 mL/min.
Fig. 4. (a) Concentrations of acyclic acid with varied residence times at different
initial K2S2O8 concentrations; (b) linear fitting of log[KBS]0M with log k[KBS]0Mn2.
Other experimental details are [AA]0 = 1.40 mol/L, QAA = 30 mL/min, QKBS = 10 mL/
min, T = 95 C, and QCW = 10 mL/min.
n1 1AAn1 1 KBSn2
After carefully controlling the mixing performance in the
microreactor platform, the reaction kinetics were studied. The
half-life of K2S2O8 is 12 min at 95 C, and the blank titration in
the analysis of AA concentration indicated that the K2S2O8 concentration decreased less than 5% after the reaction; thus, the reduction of K2S2O8 in the microreactor platform was negligible.
Fig. 3a shows the AA conversions at different initial concentrations.
The conversion increased quickly at higher initial concentrations,
indicating that the order of [AA] is higher than 1. Fig. 3b shows
the rates of polymerization (log Rp), and the linear fitting in this figure gives an order of 1.41, which is different from other free radical
polymerization kinetics such as styrene, whose monomer order is
1.0 theoretically [38]. Previous studies suggested that the order
of AA is 1.5 in theory, owing to the secondary monomerenhanced decomposition of the initiator [31]. The measured order
of AA in this study almost fits well with the intrinsic kinetic
parameter.
Based on the approximation that the exact order of AA is
n1 = 1.5, the effects of initiator concentration were evaluated.
According to classical principles [32], the chain initiation is the rate
determining step. As expected, polymerization speeds up at higher
initiator concentrations. Since the concentration of K2S2O8 is
almost constant during the reaction, different K2S2O8 concentrations would reveal the kinetic parameter of the initiator. Fig. 4
AA0:5
1
AA0:5
0M
1
n1 1
2
n1 1AA0M
KBSn0M
kt
k
2
KBSn0M
t
2
where [AA]0M and [KBS]0M are the concentrations of acrylic acid and
K2S2O8 after mixing ([AA]0M = [AA]0QAA/(QAA + QKBS), [KBS]0M =
[KBS]0QKBS/(QAA + QKBS)). With the slopes in Fig. 4a, the n2 value
was confirmed. The reaction rate constant could be drawn on the
basis of the above results. As shown in Table 2, the calculated
results fit with each other, proving that the results were reliable.
Here, the reaction temperature can be easily changed by regulating hot-water baths 14. As shown in Fig. 5, the reaction rate
increases significantly with elevated temperatures. In this case,
Table 2
Reaction rate constants at 95 C.
[AA]0 (mol/L)
[KBS]0 (mol/L)
k [L/(mol s)]
0.35
0.70
1.05
1.40
1.40
1.40
0.056
0.056
0.056
0.028
0.056
0.112
0.2577
0.2471
0.2524
0.2650
0.2647
0.2650
238
was in accord with the reported data, which ranged from 40 and
98 kJ/mol. Lorber et al. [35] gave an explanation for the varied activation energies based on the complexity of polymerization. They
reported that the reaction rate might become monomer
diffusion-limited with the generation of polymers at the end of
the reaction process. Since the AA concentrations in this study
were much lower those reported previously (24 mol/L) [39,30],
the results in this study should be more accurate.
As a brief summary, the kinetic equation for the AA polymerization reaction under the above experimental conditions is expressed
as
!
dAA
6:74 104
8
AA1:5 KBS0:5
8:0 10 exp
dt
RT
The advantages of the microreactor in measuring polymerization kinetics are obvious. Usually, it is very difficult to collect samples from batch reactors in less than 1 min, where the reactant
mixing is not complete. However, a microreactor can easily provide
data on the second time scale, since the reactant mixing is complete within several milliseconds [34]. Most kinetic parameters
are collected from low temperature batch reactors, but with the
microreactor platform it is much easier to obtain the kinetic
parameters for fast polymerization reactions at high temperatures,
where the reactant concentration changes drastically.
4.3. Molecular weight distributions
Fig. 5. (a) Concentrations of AA and K2S2O8 at different temperatures; (b) the linear
fitting of ln k with T1. Other experimental details are [AA]0 = 0.70 mol/L,
[KBS]0 = 0.056 mol/L, QAA = 30 mL/min, QKBS = 10 mL/min, and QCW = 10 mL/min.
Table 3
GPC results of the PAA products at the longest residence time in each test.*
[AA]0 (mol/L)
[KBS]0 (mol/L)
T (C)
Mn
PDI
1.40
0.028
0.056
1.112
95
162,099
129,016
106,445
2.10
2.30
2.32
0.70
1.05
1.40
0.056
95
103,326
129,016
171,934
2.42
2.30
2.34
1.40
0.056
80
85
90
95
176,052
145,781
140,415
129,016
2.03
2.09
2.08
2.30
One of the other advantages of using microreactors is the wellcontrolled molecular weight of the product, which has been
reported previously [2,10]. GPC analyses of the PAA samples at
the longest reaction time (out of tube V9) summarize the variation
in PAA molecular weight. As shown in Table 3, the number average
molecular weights (Mn) ranged from 1.03 105 to 1.76 105. The
microreactor platform works well for this reaction with macromolecules, which may open new applications in kinetics research.
The polydispersity indexes (PDI) ranged from 2.0 to 2.4 in this
experiment and were mainly affected by the reaction temperature.
5. Conclusions
The reaction kinetics of AA polymerization were carefully investigated using a microreactor platform. The microreactor platform
could suitably mix the monomer and imitator solutions at flow
rate greater than 40 mL/min. An advantage of this microreactor
platform is the easily assembled reaction tubes, when combined
with the switch-on valves, which can provide variable reaction
times. The highly exothermic free radical polymerization was conducted isothermally at temperatures ranging from 80 to 95 C. The
kinetic orders of AA and potassium persulfate, 1.5 and 0.5 respectively, were in accord with the reported kinetic parameters. The
measured activation energy was 67.4 kJ/mol, which was also in
accord with the literature value. The molecular weights of PAA produced in the platform ranged from 1.03 105 to 1.76 105 with
PDIs from 2.0 to 2.4. In addition, the advantages of the microreactor for studying the kinetics of free radical polymerization reactions, including accurate reaction time and temperature control,
as well as rapid mixing of reactants, were clarified.
Acknowledgement
We gratefully acknowledge the National Natural Science Foundation of China (91334201), the Foundation for the Author of
National Excellent Doctoral Dissertation of the Peoples Republic
of China (FANEDD 201349) and the Tsinghua University Initiative
Scientific Research Program for their support of this work.
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