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Procedia
Engineering
Procedia Procedia
Engineering 00 (2011)
Engineering 18000–000
(2011) 353 – 357
www.elsevier.com/locate/procedia

The Second SREE Conference on Chemical Engineering

Effect of Temperature on Emulsion Polymerization of n-Butyl

Acrylate
Guangfeng WU a, Chunyan WANG, Zhiyong TAN, Huixuan ZHANG
Synthetic Reins and Special Fiber Engineering Research Center, Ministry of education, Changchun University of Technology,
Changchun, 130012, China
a
gfwu@mail.ccut.edu.cn

Abstract

Poly (n-butyl acrylate) was synthesized by emulsion polymerization using CHP-Ferrous sulfate redox system as
initiator. The effect of reaction temperature on the polymerization rate and particle size (D) was studied. The reaction
showed a relatively high rate and reached high conversion in short time. The particle size was dependent on the
reaction temperature. The size of particle reduced from 95nm to 65nm when the reaction temperature changed from
20oC to 70oC with fixed polymerization conditions. The activation energy is 29.80kJ/mol.

© 2010 Published by Elsevier Ltd. Selection and/or peer-review under responsibility of Society for
Resources, Environment and Engineering

Keywords: Emulsion polymerization, n-butyl acrylate, redox initiator, kinetics.

1. Introduction

Acrylates are usually used as the polymerization monomer. And n-butyl acrylate is one of the most
widely used acrylates. Emulsion polymerization is the widely used synthesis method. Acrylic latexes are
intensively used as varnishes, paint or adhesives. The rubber was applied in all kinds of high temperature,
or oilness environment. It is necessary to control the molecular weight distribution, the gel fraction and
other characters because the structure performances affected the application.
The molecular weight distribution can be controlled by injecting chain-transfer agent [1～3] and the
changing of temperature and the initiator concentration [4～5] during the emulsion polymerization of n-
butyl acrylate. At present, potassium persulphate is widely used to be the initiator for emulsion
polymerization of n-butyl acrylate in high temperature. However, the knowledge of the kinetics,
molecular weight distribution, gel fraction, and branching [6～8] is scarce.

1877-7058 © 2011 Published by Elsevier Ltd.

doi:10.1016/j.proeng.2011.11.056
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Author name /WU et al. / Engineering
Procedia Procedia Engineering
00 (2011) 18 (2011) 353 – 357
000–000

In this work, the effect of the temperature on the rate of polymerization, particle size during the emulsion
polymerization of n-butyl acrylate with the redox system as initiator was investigated.

2. Experimental Section

2.1. Materials

n-Butyl acrylate (BA) for analysis was purified by distilling in vacuum before use. Sodium lauryl
sulfate (SDS), ferrous sulfate (FeSO4·7H2O), sodium formaldehyde sulfoxylate (SFS), ethylene diamine
tetraacetic acid(EDTA), Diisopropylbenzene hydroperoxide(CHP) and hydroquinone used were analytical
grade. These were used without any further purification. Deionized water was used to prepare all
solutions.

2.2.Polymerizations

The polymerization was carried out in a glass reactor fitted with a reflux condenser, a sampling device
and a nitrogen inlet. The experimental procedure was as follows: the aqueous solution of EDTA and
FeSO4·7H2O were initially charged into the reactor together with the solution of SDS and SFS. The
reactor was heated to the set temperature. Keeping the nitrogen inlet for about 30 min to deaerated the
oxygen from the system. The monomer and oxidizing agent were injected at the same time. The poly (BA)
latex was coagulated by aluminum muriate aqueous, and dried at 60oC in an oven. The recipe was shown
in Table 1.

Table 1. Recipe of polymerization

Ingredient Dosage/(g)
Initial part DDI 300
SDS 1.4
EDTA 0.1
FeSO4 0.01
CHP 0.2
SFS 0.5
Incremental feeding part BA 100

2.3.Characterization

Samples were withdrawn from the reactor at appropriate intervals aliquots, and inject a small amount
of hydroquinone, to prevent further polymerization. The conversion was measured gravimetrically and
using the following formula:
( M 2  M 3 ) /( M 1 - M 3 )
x(%)   100%
Wm (1)
 Guangfeng WU et/ al.
Author name / Procedia
Procedia Engineering
Engineering 18 (2011)
00 (2011) 353 – 357
000–000 3355

Where the M1, M2, M3 are the amount of the sample, the weight of dried sample and the buffer in the
sample; Wm is the monomer fraction for the monomer percentage in the reactor. The rate of
polymerization was calculated from the slope of the conversion-time curve.
dx
R p  M 0 
dt (2)
Plus-90 Laser Particle Size Analyzer was used for particle size measurement.

3.Results and Discussion

Fixed the polymerization condition, the effect of the temperature on the polymerization rate and the
particle size were studied.

3.1.Effect of temperature on the polymerization rate

Four experiments were carried out at different temperature and Fig. 1 presents the polymerization
conversion versus time at different temperature. The range is from 20oC to 70oC. All the runs showed
high polymerization rates. The conversion reached the high value of about 95% within 20 min. Then the
conversion increase leveled down. The higher the temperature is, the sooner the conversion reached the
high value. The redox system used is a diffusion controlled system but not temperature controlled system.
So the runs at different temperature show no different polymerization rate. But the increase of
temperature reduced the induction period. The run at higher temperature reached the high value for
sooner.

100

80
Conversion(%)

60

20℃
40 30℃
50℃
20 70℃

0
0 20 40 60 80 100 120
t (min)

Fig. 1, Effect of temperature on polymerization conversion

4356 Guangfeng
Author name /WU et al. / Engineering
Procedia Procedia Engineering
00 (2011) 18 (2011) 353 – 357
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2.0

1.5

lnRp (mol/L min)

1.0

0.5

0.0

2.8 2.9 3.0 3.1 3.2 3.3 3.4 3.5

-1 -1
T × 10-3(K )

Fig. 2, Relationship between reaction rate and temperature

The rate of polymerization was calculated by the formula (2). [M0] is the initial monomer
concentration and dx/dt is the slope of the conversion-time curve. Construct the relationship between ㏑
Rp and T-1 (Fig. 2), in accordance with the Arrhenius relation expression, the activation energy is
29.80kJ/mol.

3.2.Effect of temperature on the particle size

Fig. 3 shows the particle size of poly n-butyl acrylate at different temperature. The higher the
temperature is, the smaller the particle size is. The size of the latex particle decreased from 95nm to 65nm,
when the temperature increased from 20oC to 70oC. The speed of the free radical creating increased
because of the higher temperature, lead to the augment of the free radical concentration in the aqueous
phase. The increase of the rate that free radical spread to the emulsion particle from the aqueous phase
induced the enhanced nucleation rate. The number of the particles increased and the particle size
decreased.
 Guangfeng WU et/ al.
Author name / Procedia
Procedia Engineering
Engineering 18 (2011)
00 (2011) 353 – 357
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100

80

Particle size (nm)

60

40

20

0
20 30 50 70
T (oC)

Fig. 3, Particle size of poly n-butyl acrylate latex at different temperature

4.Conclusions

Emulsion polymerization of n-butyl acrylate initiated by CHP-Ferrous sulfate redox system was
investigated. With the fixed polymerization condition, the particle size decreased with the increase of
temperature. When the temperature increased from 20oC to 70oC, the particle size decreased from 95nm
to 65nm, and the activation energy is 29.80kJ/mol.

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